Dyeing composition comprising a thiol/disulphide fluorescent colorant having an external cationic charge, and method for lightening keratin materials using said colorant

Translation of description of equivalent WO 2007110534 A2

DYE COMPOSITION CONTAINING A FLUORESCENT DYE

p0002THIOL / DISULPHIDE, EXTERNAL CATIONIC CHARGE, PROCESS FOR LIGHTENING KERATIN MATERIALS FROM THIS

DYE

p0004The invention relates to the dyeing of keratin fibers using fluorescent dyes of thiol / disulfide external cationic charge.

p0005It is known to dye keratin fibers, particularly human, by direct dyeing. The process conventionally used in direct dyeing comprises applying to the keratin fibers direct dyes, which are colored and coloring molecules that have affinity for the fibers, allowing them to diffuse and then rinsing the fibers.

p0006The direct dyes which are conventionally used are for example dyes of the nitrobenzene type, anthraquinone dyes, nitropyridine dyes of the azo, xanthene, acridine, azine or triaryl methane.

p0007The colorations resulting from the use of direct dyes are temporary or semi-permanent colorings since the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption from the surface and / or the heart of the fiber are responsible their low dyeing power and their poor resistance to washing or perspiration.

p0008Furthermore, the dyeing of keratinous fibers from conventional direct dyes does not allow to significantly lighten keratin fibers.

p0009The lightening of the color of keratin fibers, especially dark to lighter shades, by optionally modifying the shade thereof, constitutes an important demand.

p0010Conventionally, to obtain a lighter coloring implements a chemical bleaching process. This method comprises treating keratin materials such as keratin fibers, in particular hair, with a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, usually under alkaline conditions.

p0011This bleaching system has the disadvantage of degrading keratin materials, especially keratin fibers, especially human, such as hair and of impairing their cosmetic properties. The fibers have a tendency to become rough, more difficult to disentangle and more brittle. Finally, enlightenment or bleaching keratin fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in hair straightening treatments.

p0012Another lightening technique comprises applying dark hair fluorescent direct dyes. This technique, described in particular in documents FR 2830189 and WO 2004/091473 allows to respect the quality of the keratin fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampoos.

p0013To increase the toughness of direct dyeing, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react with reactive groups in dyes residues cystine or cysteine ​​in many keratin fibers see for example the Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2,024,509.

p0014Furthermore it is known to protect or thiol functions in one molecule to be grafted to the hair before applying them said WO99 / ​​51194 hair. However, this application does not mention the use of fluorescent dyes for coloring or lighten hair.

p0015Other disulphide dyes known for coloring keratin fibers are disulphide derivatives of aminothiophenol derivatives. Such dyes are described for example in patent FR 1156407. These dyes may be used under relatively mild conditions in the presence of a slightly reducing medium or after a reducing pre-treatment of the hair. However, these dyes can cause colourshifts when applying.

p0016Finally, WO 2005/097051 describes the document disulfide dyes aza imidazoliums for the direct dyeing of keratin fibers.

p0017The object of the present invention is to provide new dyeing keratin materials systems in particular human keratin fibers, in particular hair, which do not present the drawbacks of the existing bleaching processes. In particular, an object of the present invention is to provide direct dyeing systems for obtaining lightening effects especially on naturally or artificially dark keratin fibers, stubborn face successive shampoos that do not degrade the keratin fibers and that do not alter their cosmetic properties. This object is achieved with the present invention which relates to a keratinous material dyeing process, in particular keratin fibers, especially human such as the hair, especially dark hair, consisting in applying to keratin materials, a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye pyridinium external cationic charge selected from the dyes of formulas (I) or (II):

p0018<img id="imgf000004_0001" he="46" wi="150" file="imgf000004_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> the organic or mineral acid salts, optical isomers, geometrical isomers, and solvates such as hydrates;

p0019formulas (I) or (II) wherein:

p0020> R_at and R '_at, Identical or different, represent an aryl group (-C C₄) Alkyl or a (C_rC₆) Alkyl optionally substituted by hydroxyl or amino, -C₄ alkylamino, (Ci-C₄) Dialkylamino, said alkyl radicals possibly forming with the nitrogen atom which bears them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom identical to or different from nitrogen; preferably R_at and / or R '_at represent a group (-C₃) Alkyl optionally substituted by hydroxy, or a benzyl group;

p0021> R_b and R '_b, Identical or different, represent a hydrogen atom, an aryl group (-C₄) Alkyl or a (C₁-C₆) Alkyl optionally substituted; including R_b and / or R '_b represent a hydrogen atom or a (C₁-C₃) Alkyl or benzyl;

p0022> R₉, R '_g, R "_g and R " '_g, Identical or different, represent a hydrogen atom, an amino group, (C₁-C₄) Alkylamino, (C₁-C₄) Dialkylamino, trifluoromethyl, acylamino, (C_rC₄) Alkoxy (C_rC₄) Alkylcarbonyloxy, (-C₄) Alkoxycarbonyl, (-C₄) Alkylcarbonylamino, (-C₄) Alkylsulfonylamino, a (C₁-C₃Kyle JHA; > R_hj R '_hj R "_h and R " '_hj identical or different, represent a hydrogen atom, a halogen atom, a dialkylamino group (Ci-C₄), (C₁- C₄) Alkylcarbonylamino, acylamino, (C_rC₄) Alkylsulfonylamino, or a (Ci-C₄) Alkyl; particularly R_h, R'H, R "h and R" '_h represent a hydrogen atom, or a (CrC₃) Alkyl;

p0023> Or else two groups R₉ and R '_g; R "_g and R " '_g ; R_h and R '_h ; R "_h and R " '_h carried by two adjacent carbon atoms, together form a benzo, indeno, heterocycloalkyl fused or fused heteroaryl; the benzo, indeno, heterocycloalkyl or heteroaryl being optionally substituted by a halogen atom, an amino group, (C₁-C₄) Alkylamino, (C_rC₄) Dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, alkoxy, C_rC₄(Poly) hydroxyalkoxy, C₂-C₄(C_rC₄) Alkylcarbonyloxy (C₁- C₄) Alkoxycarbonyl, (-C₄) Alkylcarbonylamino, acylamino, carbamoyl, (C_rC₄) Alkylsulfonyl-amino, aminosulfonyl, or a (Ci-Ci₆) Alkyl optionally substituted by a group selected from (CRCI₂) Alkoxy, hydroxy, cyano, carboxy, amino, (Ci-C₄) Alkylamino and (C₁- C₄) Dialkylamino, or else the two alkyl radicals borne by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom; particularly R₉ and R '_g ; R "_g and R " '_g together form a benzo group;

p0024> R, R ', R "ι and R" i are identical or different, represent a hydrogen atom, or a (dC₄) Alkyl; especially a hydrogen atom;

p0025> Ri, R₂R 3, R₄, R ', R'₂, R '3 and R'₄, Identical or different, represent a hydrogen atom or a (C₁-C₄) Alkyl preferably R₁, R₂R3_> R₄, R '_> R'2_> R '3 and R'₄ represent a hydrogen atom;

p0026> <^•-^{* **}-, Present or absent, represents a benzo group;

p0027> T_at and T_b, Identical or different, represent: i) a σ covalent bond; ii) a radical selected from -N (R) -, -N⁺(R) (R⁰) -, With R, R °, identical or different, representing a hydrogen atom, an alkyl radical C₁-C₄Hydroxyalkyl, C₁-C₄; or aryl (C_rC₄) Alkyl, iii) a heterocycloalkyl or heteroaryl radical, cationic or noncationic, preferably monocyclic, containing one or two heteroatoms, especially two nitrogen atoms, and especially containing from 5 to 7 members such as imidazolium; or a saturated 6-membered ring:

p0028<img id="imgf000006_0001" he="30" wi="133" file="imgf000006_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0029CH₂, NR ° wherein R ° is as defined above and An^" represents an anionic ion-against; preferentially T_at and T_b represent a covalent bond;

p0030> M, m ', n and n', identical or different, represent an integer ranging from 0 to 6 with m + n and m '+ n', identical or different, represent an integer ranging between 1 and 10; particularly m + n = m '+ n' is an integer ranging between 2 and 4; preferentially when T_at and T_b represent a σ covalent bond, m + n = m '+ n' is an integer equal to 2;

p0031> Where T_at represents a σ covalent bond, Y represents a group selected from: o optionally substituted aryl such as phenyl, dibenzosuberyl, or 1, 3,5-cycloheptatrienyl; o optionally substituted heteroaryl including aromatic, cationic or non containing from 1 to 4 heteroatoms such as: i) monocyclic heteroaryl of 5, 6 or 7 membered ring 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, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tétrazinium, azepine, azépinium, oxazepinyl, oxazépinium, thiepinyl, thiépinium, imidazolyl, imidazolium; ii) heteroaryl bicyclic 8- to 11-membered ring such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyle, benzothiazolyl, benzothiazolium pyridoimidazolyle, pyridoimidazolium, thiénocycloheptadiényle, these monocyclic or bicyclic groups being optionally substituted by one or more groups such as (CrC₄) Alkyl such as methyl, or polyhalo (C_rC₄) Alkyl such as trifluoromethyl; iii) heteroaryl or tricyclic ABC:

p0032<img id="imgf000007_0001" he="17" wi="37" file="imgf000007_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein both rings A, G optionally comprises a heteroatom, and ring B is a 5-, 6 or 7-membered, particularly 6-membered and contains at least one heteroatom as piperidyl or pyranyl; o optionally substituted heterocycloalkyl, optionally cationic, heterocycloalkyl particular group is a monocyclic saturated or partially saturated 5-, 6- or 7-membered ring comprising 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl, di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyle, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl di / tetrahydropyrimidinyl, these groups being optionally substituted by one or more groups as (C_rC₄) Alkyl, oxo or thioxo; or heterocycle represents the following group:

p0033<img id="imgf000007_0002" he="34" wi="42" file="imgf000007_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R '^c, R '^d, R '^Θ, R '^f, R '⁹ and R '^h, Identical or different, represent a hydrogen atom or an alkyl group, or else two groups R '⁹ R '^hAnd / or R '^Θ R '^f form an oxo or thioxo, or else R '⁹ R '^Θ together form a cycloalkyl; and v represents an integer ranging between 1 and 3; preferably, R '^c to R '^h represent an atom hydrogen; and An^" represents an anionic ion-against; o (di) arylalkyl optionally substituted such as 9-anthracenylmethyl, diphenylmethyl or phenylmethyl optionally substituted by one or more groups chosen in particular from (CrC₄) Alkyl, (-C₄) Alkoxy such as methoxy, hydroxy, (C_rC₄) Alkylcarbonyl ,, (di) (-C₄) (Alkyl) amino such as dimethylamino; o (di) heteroarylalkyl optionally substituted, the heteroaryl group is in particular cationic or non monocyclic having 5 or 6 ring members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium or triazinyl optionally substituted by one or more group such as (CrC₄) Alkyl especially methyl, preferably (di) heteroarylalkyl is (di) heteroarylmethyl or (di) heteroarylethyl; o cyclic sterically hindered such as adamantyl;

p0034> Where T_at represents -N (R) -, -N⁺(R) (R⁰) -, Heterocycloalkyl or heteroaryl radical, cationic or non; 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^αR^βR^γR^δ or a phosphonium group: P⁺R^αR^βR^γR^δ with R^α, R^β, R^γ and R^δIdentical or different, representing a hydrogen atom or a group (-C₄) Alkyl; or v) a protective group of thiol; and

p0035> M¹ representative against an anionic ion; provided that when the compound of formula (I) or (II) contains other cationic parts, it is associated with one or more anionic against ions to achieve electroneutrality of the formula (I) or (II ).

p0036Another object of the invention is a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye selected from the dyes of formula (I) or (II) as defined above, and optionally a reducing agent.

p0037The invention also relates to novel fluorescent dyes of formula (I) or (II) as defined above. The dyeing process according to the invention allows to visibly color dark keratin materials, in particular dark human keratin fibers, especially dark hair.

p0038Furthermore, the process of the invention allows to obtain a dyeing of keratin materials, in particular human keratinous fibers, especially hair, without damaging said material, volatile vis-a-vis of shampoos, common attacks (sun, perspiration ), and other hair treatments. The method of the invention also provides a lightening of keratin materials such as keratin fibers, particularly dark keratin fibers and more particularly dark hair.

p0039Within the meaning of the invention, the term dark keratin material which exhibits a lightness L * measured in the CIE L * a * b * less than or equal to 45 and preferably less than or equal to 40, given that, moreover L * = 0 is equivalent to black and L * = 100 to white.

p0040Within the meaning of the invention, the term hair naturally or artificially dark hair whose tone height is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut).

p0041The lightening of the hair is evaluated by the variation in "tone height" before and after application of the compound of formula (I) or (II).

p0042The notion of "tone" is based on the classification of natural shades, one tone separating each shade from the following or preceding immediately. This definition and classification of the natural shades are well known to hair styling professionals and published in the book "Science of hair treatment" by Charles Zviak 1988 Ed. Masson, p. 215 and 278.

p0043The tone heights range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the number, the higher the grade is clear.

p0044An artificially colored hair is a hair whose color has been modified by for example a dyeing treatment, a dyeing with direct dyes or oxidation dyes.

p0045Preferably, the composition should, after application to the hair, for example chestnut, bring the results below.

p0046We are interested in hair reflectance performance when irradiated with visible light in the wavelength range from 400 to 700 nanometers. - It then compares the reflectance curves as a function of wavelength, of hair treated with the composition of the invention and the untreated hair.

p0047- The curve corresponding to the treated hair should show a reflectance in the range of wavelengths from 500 to 700 nanometers higher than the curve corresponding to the untreated hair.

p0048This means that in the range of wavelength from 540 to 700 nanometers, there is at least a range where the reflectance curve corresponding to the treated hair is higher than the reflectance curve corresponding to the untreated hair. The term "higher" is a difference of at least 0.05% reflectance and preferably at least 0.1%. This does not exclude that there may be in the wavelength range from 540 to 700 nanometers, at least a range where the reflectance curve corresponding to the treated hair is superimposable or lower than the reflectance curve corresponding to untreated hair. Preferably, the wavelength at which the difference is between the maximum reflectance curve of the treated hair and of the untreated hair is in the wavelength range from 500 to 650 nanometers, and preferably in the wavelength range of 550-620 nanometers.

p0049Within the meaning of the present invention, and unless a different indication is given: the radicals "aryl" or "heteroaryl" may be substituted by at least one substituent on a carbon atom selected from:

p0050• an alkyl radical C1-C16, preferably Ci-Ce; . a halogen atom such as chlorine, fluorine or bromine;

p0051• a hydroxyl group;

p0052. alkoxy C₁-C₂ ;

p0053• a radical alkylthio, C₁-C₂ ;

p0054. a radical (poly) hydroxyalkoxy C₂-C₄ ;

p0055• an amino radical;

p0056• an amino radical substituted by one or two alkyl radicals, identical or different, in dC₆ optionally bearing at least: i) hydroxy, ii) an amino group;

p0057• acylamino (-NR-COR ') wherein the radical R is an atom hydrogen, alkyl dC₄ optionally bearing at least one hydroxyl group and the radical R 'is alkyl C₁-C₂ ; . a carbamoyl radical ((R)₂N-CO-) in which the radicals R, identical or different, represent a hydrogen atom, an alkyl radical Ci-C₄ optionally bearing at least one hydroxyl group;

p0058• an alkylsulfonylamino (R¹SO₂-NR-) In which the radical R represents a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical -C₄ ;

p0059• an aminosulfonyl radical ((R)₂N-SO₂-) Wherein the radicals R, identical or different, represent a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group;

p0060• a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);

p0061• a cyano group;

p0062. a polyhaloalkyl group having 1 to 6 carbon atoms and 1 to 6 halogen atoms, identical or different, the polyhaloalkyl group is for example trifluoromethyl;

p0063- The cyclic or heterocyclic part of a non aromatic radical may be substituted by at least one substituent on a carbon atom selected from the groups:. hydroxy,

p0064• C₁-C₄,. alkoxy, C₁-C₄,

p0065• (poly) hydroxyalkoxy, C₂-C₄,. alkylthio C₁-C₂ ;

p0066• RCO-NR'- wherein the radical R 'is a hydrogen atom or an alkyl radical C₁-C₄ and the radical R is a hydrogen atom, an alkyl radical C₁-C₂Or amino substituted with two alkyl groups are identical or different C₁-C₄ said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or may not be nitrogen;

p0067• RCO-O- wherein the radical R is an alkyl radical C₁-C₄, amino substituted with two alkyl groups are identical or different -C₄, Said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or may not be nitrogen;

p0068• RO-CO- group wherein R is an alkyl radical -C₄And amino substituted with two alkyl groups are identical or different C₁-C₄ said alkyl radicals possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom or may not be nitrogen;

p0069- An "aryl" radical represents a monocyclic or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and at least one ring is aromatic; preferably the aryl is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;

p0070- A "diarylalkyl" radical represents a group having the same carbon atom of an alkyl group, two aryl groups, which are identical or different, such as diphenylmethyl or 1,1-diphenylethyl;

p0071- A "heteroaryl radical" represents a monocyclic or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members and from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and at least one ring is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phénooxazolyle, pyrazinyl, pyrazolyl, pyrilyle, pyrazoyltriazyle, pyridyl, pyridinoimidazolyle, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyle, thiopyrylyle, triazolyl, xanthylyle and its ammonium salt;

p0072- A radical "diheteroarylalkyl" represents a group comprising, on the same carbon atom of an alkyl group, two heteroaryl groups, which are identical or different, such as difurylmethyl, 1, 1-difurylethyl, dipyrrolylmethyl dithienylmethyl;

p0073- A "cyclic group" is a non-aromatic cycloalkyl, mono- or polycyclic, condensed or not, containing from 5 to 22 carbon atoms, which may contain 1 or more unsaturations; particularly the cyclic radical is a cyclohexyl;

p0074- A radical "sterically hindered cyclic group" is a cyclic radical, aromatic or nonaromatic, substituted or unsubstituted, hindered by steric effect or stress, comprising 6 to 14 members, which may be bridged by way of sterically hindered radicals, bicyclo include [1.1.0] butane, the mésytyles such as 1, 3,5 triméthylpnényle, 1,3,5-triterbutylphényle, 1, 3,5-isobutylphenyl, the trimétylsillylphényle 1,3,5 and adamantyl ;

p0075- A "heterocyclic group" is a non-aromatic radical mono- or polycyclic, condensed or not, containing from 5 to 22 members and having from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium ;

p0076- An "alkyl group" is a hydrocarbon radical CRCI₆Linear or branched, preferably dC₈ ;

p0077- The expression "optionally substituted" assigned to the alkyl radical implies that said alkyl radical may be substituted by one or more radicals chosen from the radicals: i) hydroxy, ii) alkoxy, -C₄Iii) acylamino, iv) amino optionally substituted by one or two alkyl radicals, identical or different C_rC₄, Said alkyl radicals possibly forming with the nitrogen atom carrying them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom identical to or different from nitrogen;

p0078- A "alkoxy radical" is an alkyl-oxy radical or alkyl-O- in which alkyl is a hydrocarbon radical, linear or branched C₁-C₁₆ preferably C₁-C₈ ;

p0079- A "alkylthio" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched C₁-C₁₆ preferably C₁-C₈ ; the limits delimiting the extent of a range of values ​​are included in this range; an "organic or mineral acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H₂SO₄, Iv) alkylsulfonic acids: AIk-S (O)₂OH such as methylsulphonic acid and ethylsulphonic acid; v) arylsulfonic acids: Ar S (O)₂OH such as benzenesulfonic and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) of alcoxysulfiniques acids: Alk-OS (O) OH such as from methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulphinic acids such as tolueneoxysulphinic phenoxysulphinic acid and acid; xii) phosphoric acid H₃PO₄; xiii) of acetic acid CH₃COOH; xiv) of triflic acid CF₃SO₃H xv) tetrafluoroboric acid HBF₄ ; a "against anionic ion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly against the anionic ion is selected from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including the C₁-C₆ alkylsulphonates: Alk-S (O)₂O^" such as methyl sulfonate or mesylate and ethyl sulfonate; iv) arylsulfonates: Ar-S (O)₂O^" such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkylsulfites: Alk-OS (O)^" such as méthysulfite and éthylsulfite; x) arylsulfites: Ar-OS (O)^" such as benzènesulfite and toluènesulfite; xi) alkyl sulfates: Alk-OS (O)₂O^" such as methyl sulfate and ethyl sulfate; xii) arylsulfates: Ar-OS (O)₂O^"Xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

p0080Fluorescent dyes of formula (I) or (II) are compounds capable of absorbing in the UV or visible radiation at a wavelength λ_abs between 250 and 800 nm and capable of réémettrent in the visible range at a transmission wavelength λ_em between 400 and 800 nm.

p0081Preferably the fluorescent compounds of formula (I) or (II) are dyes capable of absorbing in the visible, λ_abs between 400 and 800 nm and re-emitting in the visible, λ_em between 400 and 800 nm. More particularly the fluorescent dyes are dyes capable of absorbing at a wavelength λ_abs between 420 nm and 550 nm and re-emitting in the visible range at a wavelength λ_em between 470 and 600 nm.

p0082A particular embodiment of the invention relates to dyes of formula (I) or (II) wherein T_atT_b represent -N (R) -, -N⁺(R) (R⁰) -, Heterocycloalkyl or heteroaryl radical, cationic or non. More particularly the thiol fluorescent dyes of formula (II) according to SY then comprise a group Y which represents an atom hydrogen or an alkali metal, preferably, Y represents a hydrogen atom.

p0083According to another particular embodiment of the invention, in formula (II) above wherein T_at represents -N (R) -, -N⁺(R) (R⁰) -, Y is a protecting group and the protecting group is selected from those known by the skilled artisan such as those described in the literature "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed, NY. 1981, pp.193-217; "Protecting Groups" P. Kocienski, Thieme, 3^èmΘ ed., 2005, c. 5.

p0084The fluorescent compounds of the invention of formula (II) contain an SY function which may be in the covalent form -S-Y or -S ionic^" Y⁺ depending on the nature of Y and of the pH of the medium.

p0085Especially when Y represents a group protecting the thiol function of the compound of formula (II), Y is selected from the following radicals:

p0086> (C_rC₄) Alkylcarbonyl;

p0087> (C_rC₄) Alkylthiocarbonyl;

p0088> (C_rC₄) Alkoxycarbonyl;

p0089> (-C₄) Alkoxythiocarbonyl;

p0090> (C_rC₄) Alkylthio-thiocarbonyl;

p0091> (Di) (-C₄) (Alkyl) aminocarbonyl;

p0092> (Di) (-C₄) (Alkyl) aminothiocarbonyl;

p0093> Arylcarbonyl as phenylcarbonyl;

p0094> Aryloxycarbonyl;

p0095> Aryl (-C₄) Alkcoxycarbonyle;

p0096> (Di) (-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl;

p0097> (-C₄) (Alkyl) arylaminocarbonyl;

p0098> Carboxy;

p0099> SO₃^" ; M⁺ with M⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (II) and M⁺ are absent;

p0100> Optionally substituted heteroaryl, including aromatic groups, cationic or non containing from 1 to 4 heteroatoms: i) monocyclic 5-, 6- or 7-membered ring 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, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tétrazinium, azepine, azépinium, oxazepinyl, oxazépinium, thiepinyl, thiépinium, imidazolyl, imidazolium; ii) bicyclic 8- to 11-membered ring such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyle, benzothiazolyl, benzothiazolium pyridoimidazolyle, pyridoimidazolium, thiénocycloheptadiényle, these monocyclic or bicyclic groups being optionally substituted by one or more groups such as alkyl such as methyl, or polyhalo as trifluoromethyl; iii) or tricyclic ABC:

p0101<img id="imgf000016_0001" he="17" wi="37" file="imgf000016_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein both rings A, G optionally comprises a heteroatom, and ring B is a 5-, 6 or 7-membered, particularly 6-membered and contains at least one heteroatom as piperidyl or pyranyl; optionally substituted heterocycloalkyl, optionally cationic, heterocycloalkyl particular group is a monocyclic saturated or partially saturated 5-, 6- or 7-membered ring comprising 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl , di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyle, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl di / tetrahydropyrimidinyl, these groups being optionally substituted by one or more groups such as alkyl , oxo or thioxo; or heterocycle represents the following group:

p0102<img id="imgf000016_0002" he="30" wi="40" file="imgf000016_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R '^c, R '^d, R '^Θ, R '^f, R '⁹ and R '^h, Identical or different, represent a hydrogen atom or an alkyl group, or else two groups R '⁹ R '^hAnd / or R '^Θ R '^f form an oxo or thioxo, or else R '⁹ R '^Θ together form a cycloalkyl; and v represents an integer ranging between 1 and 3; preferably, R '^c to R '^h represent a hydrogen atom; and An^" represents against ion;

p0103> Isothiouronium -C (NR '^cR '^d) = N⁺R '^ΘR '^f; Year^" R '^c, R '^d, R '^Θ and R '^f, Identical or different, represent a hydrogen atom or an alkyl group; preferably, R '^c to R '^f represent a hydrogen atom; and An^" represents against ion;

p0104> Isothiourea -C (NR '^cR '^d) = NR '^Θ R '^c, R '^d, R '^Θ are as defined above;

p0105> (Di) arylalkyl optionally substituted such as 9-anthracenylmethyl, diphenylmethyl or phenylmethyl optionally substituted by one or more groups chosen in particular from alkyl, alkoxy such as methoxy, hydroxy, alkylcarbonyl ,, (di) (alkyl) amino such as dimethylamino;

p0106> (Di) heteroarylalkyl optionally substituted, the heteroaryl group is in particular cationic or non monocyclic having 5 or 6 ring members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium or triazinyl optionally substituted by one or more group such as especially methyl alkyl, preferably (di) heteroarylalkyl is (di) heteroarylmethyl or (di) heteroarylethyl;

p0107> CR¹¹R¹²R '³ R '¹, R '² and R '³ identical or different, representing a halogen atom or a group selected from:

p0108• optionally substituted alkyl such as methyl, ethyl;

p0109• optionally substituted alkoxy such as methoxy or ethoxy;

p0110• optionally substituted aryl such as phenyl optionally substituted with one or more groups such as alkyl, alkoxy, hydroxy;

p0111• optionally substituted heteroaryl, such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted with alkyl;

p0112> P (Z¹) R "¹R "²R "³ R "¹And R "² identical or different, represent a hydroxyl group, alkoxy or alkyl, R "³ represents hydroxy or alkoxy, and Z¹ represents an atom of oxygen or sulfur;

p0113> Hindered cyclic; and

p0114> Optionally substituted alkoxyalkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

p0115In particular the group Y of the fluorescent dye of formula (II) is an alkali metal or a protecting group such as:

p0116> (C_rC₄) Alkylcarbonyl such as methylcarbonyl or ethylcarbonyl;

p0117> Arylcarbonyl as phenylcarbonyl;

p0118> (C_rC₄) Alkoxycarbonyl;

p0119> Aryloxycarbonyl;

p0120> Aryl (dC₄) Alkoxycarbonyl;

p0121> (Di) (-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl;

p0122> (Ci-C₄) (Alkyl) arylaminocarbonyl;

p0123> Optionally substituted aryl such as phenyl;

p0124> Cationic monocyclic heteroaryl of 5, 6-membered ring such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted by one or more identical or different groups (dC₄) Alkyl such as methyl;

p0125> Heteroaryl cationic bicyclic 8- to 11-membered ring such as benzoimidazolium or benzoxazolium; these groups being optionally substituted by one or more identical or different groups (Ci-C₄) Alkyl such as methyl;

p0126> Cationic heterocycle of formula below:

p0127<img id="imgf000018_0001" he="28" wi="25" file="imgf000018_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0128> Isothiouronium -C (NH₂) = N⁺H₂; Year^";

p0129> Isothiourea -C (NH₂) = NH;

p0130> SO₃^"M⁺ with M⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (II) and M⁺ are absent. According to a particular embodiment, the protected thiol fluorescent dyes of formula (II) comprise a group Y i) monocyclic heteroaryl of 5 or 6 membered aromatic, cationic comprising 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, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tétrazinium, oxazépinium, thiepinyl, thiépinium, imidazolium; ii) heteroaryl bicyclic 8- to 11-membered cationic such as indolinium, benzoimidazolium benzoxazolium, benzothiazolium, these monocyclic or bicyclic heteroaryl groups being optionally substituted by one or more groups such as alkyl like methyl, or polyhalo (C₁-C₄) Alkyl such as trifluoromethyl; iii) or heterocyclic:

p0131<img id="imgf000019_0001" he="27" wi="24" file="imgf000019_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R '^c and R '^d, Identical or different, represent a hydrogen atom or a (dC₄) Alkyl; preferably, R '^c to R '^d represent a (dC₄) Alkyl such as methyl; and An- represents an against-ion.

p0132In another particular embodiment when T_atT_b represent a covalent bond. Particularly the protected thiol fluorescent dyes of formula (II) comprise a group then Y i) monocyclic heteroaryl of 5 or 6 membered aromatic, cationic comprising 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as oxazolium , isoxazolium, thiazolium, isothiazolium, 1, 2,4-triazolium or 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium , triazinium, tétrazinium, oxazépinium, thiepinyl, thiépinium, imidazolium; ii) heteroaryl bicyclic 8- to 11-membered cationic such as indolinium, benzoimidazolium benzoxazolium, benzothiazolium, these monocyclic or bicyclic heteroaryl groups being optionally substituted by one or more groups such as alkyl like methyl, or polyhaloalkyl such as trifluoromethyl; iii) or heterocyclic: <img id="imgf000020_0001" he="30" wi="27" file="imgf000020_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R '^c and R '^d, Identical or different, represent an alkyl group; preferably, R '^c to R '^d represents an alkyl group such as methyl; and An^" represents an anionic ion-against.

p0133Y particularly represents a group selected from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1, 2,3-triazolium, oxazolium 1,2,4, 1,2,4-thiadiazolium, pyrylium, pyridinium , pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted by one or more groups (-C₄) Alkyl especially methyl.

p0134According to a particular embodiment of the invention, the fluorescent dyes of the invention are of formula (Ia), (IIa), (Ib), (Mb), (Ic) or (IIc) each having an ethylene group which links the pyridinium part to the phenyl at the ortho or para position or in positions 4-4 ', 4-2' or 2-4 'for (Ia), (IIa), (Ib) or (IIb), or then in positions 4 5 '2 or 5' to (Ic) or (Mc):

p0135<img id="imgf000020_0002" he="54" wi="149" file="imgf000020_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000021_0001" he="47" wi="156" file="imgf000021_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0136(Hb)

p0137<img id="imgf000021_0002" he="51" wi="166" file="imgf000021_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> formulas (Ia) or (IIa) in which:

p0138• R¹_at and R²_at, Identical or different, represent a benzyl or alkyl group optionally substituted by a hydroxy group such as methyl, ethyl or hydroxyethyl;

p0139• R¹_b and R²_b, Identical or different, represent a hydrogen atom; benzyl or alkyl such as methyl or ethyl;

p0140• T '_at and T '_b, Identical or different, represent a σ bond; an -N⁺(R) (R⁰) - With R ° and R, identical or different, representing an alkyl group such as methyl; or when T '_at and T '_b represent an imidazolium group;

p0141• Y 'represents a group chosen from imidazolium, thiazolium; oxazolium; 1,2,4-triazolium; pyridinium; pyrimidinium; benzoxazolium and benzothiazolium; these groups being substituted by one or more groups, identical or different, alkyl group such as methyl or ethyl;

p0142• m, n, m 'and n', identical or different, represent an integer ranging between 1 and 6 with m + n = m '+ n' represent an integer ranging between 2 and 6; especially when T '_at and T '_b represent a σ bond, then m + n = m '+ n' is an integer equal to 2; • M 'represents an anionic ion-against; Formulae (Ib) or (IIb) in which:

p0143^^* R_at, R _at, R b, R b_> Rh Ri_> R ii R ii Ri, R -i, R2_> R 2_> R3J R R 3J₄JR ₄JT_at, Tb, m, m, n, n 'and Y are as defined above;

p0144> R₉ and R '_g ; R "_g and R " '_g identical or different, represent a hydrogen atom, a halogen atom, an amino group, (CrC₄) Alkylamino, (C₁-C₄) Dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, alkoxy-C₄(Poly) hydroxyalkoxy, C₂-C₄(DC₄) Alkylcarbonyloxy, (C_r C₄) Alkoxycarbonyl, (-C₄) Alkylcarbonylamino, acylamino, carbamoyl, (d- C₄) Alkylsulfonylamino, aminosulfonyl, or a radical (CRCI₆) Alkyl optionally substituted by a group selected from (C₁-C₁₂) Alkoxy, hydroxy, cyano, carboxy, amino, (C_rC₄) Alkylamino and (C_rC₄) Dialkylamino, or else the two alkyl radicals borne by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom; particularly R₉ and R '_g ; R "_g and R " '_g represent a hydrogen atom, halogen or a (C₁-C₃) Alkyl, preferably R₉ and R 'g; R "_g and R " '_g represent a hydrogen atom;

p0145> R_h and R '_h ; R "_h and R " '_h carried by two adjacent carbon atoms, together form a benzo, indeno, heterocycloalkyl fused or fused heteroaryl; the benzo, indeno, heterocycloalkyl or heteroaryl being optionally substituted by a halogen atom, an amino group, (CrC₄) Alkylamino, (-C₄) Dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, alkoxy, C₁-C₄(Poly) hydroxyalkoxy, C₂-C₄(-C₄) Alkylcarbonyloxy (-C₄) Alkoxycarbonyl, (-C₄) Alkylcarbonyl amino, acylamino, carbamoyl, (Ci-C₄) Alkylsulfonyl-amino, aminosulfonyl, or a (C_rThis₆) Alkyl optionally substituted by a group selected from (Ci-Ci₂) Alkoxy, hydroxy, cyano, carboxy, amino, (Ci-C₄) Alkylamino and (Ci-C₄) Dialkylamino, or else the two alkyl radicals borne by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom; particularly R_h and R '_h ; R "_hand R " '_h together form a benzo group; and formulas (Ic) or (IIc) wherein:

p0146> R_at, R '_at, Rb_> R'b_> Ri. R "i_> Ri _> r'i_> R2_> R'2_> R3_> R'3, R₄J R'4_> T_at, Tb, m, m ', n, n' and Y are as defined above;

p0147> R₉, R '_g, R "_g, R "_g, R_not, R '_h, R "_h and R " '_h, Identical or different, represent a hydrogen atom, a halogen atom, an amino group, (C₁- C₄) Alkylamino, (C₁-C₄) Dialkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, alkoxy, -C₄(Poly) hydroxyalkoxy, C₂-C₄(C₁- C₄) Alkylcarbonyloxy, (C_rC₄) Alkoxycarbonyl, (C_rC₄) Alkylcarbonylamino, acylamino, carbamoyl, (Ci-C₄) Alkylsulfonylamino, amino-sulfonyl, or a (C₁-C₁₆) Alkyl optionally substituted by a group selected from (C₁-C₁₂) Alkoxy, hydroxy, cyano, carboxy, amino, (C₁-C₄) Alkylamino and (C₁-C₄) Dialkylamino, or else the two alkyl radicals borne by the amino group nitrogen atom form a heterocycle comprising from 5 to 7 members and optionally comprising another heteroatom identical to or different than the nitrogen atom; particularly R₉, R '_g, R and R '_h represent a hydrogen atom, halogen or a (C₁-It) Alkyl, preferably R₉, R 'g, R_h R'n and represent a hydrogen atom; provided that when the compound of formula (Ia), (Ma), (Ib), (IIb), (Ic) or (IIc) contains other cationic parts, it is associated with one or more anionic counter ions to achieve electroneutrality of the formula (Ia), (Ma), (Ib), (Mb), (Ic) or (IIc). Another embodiment of the invention relates disulfide dyes of formula (I) symmetrical ie R_at, R_b, R₉, R '_g, R_h, R'H, R, R ', R2, R3, R₄T_at, M, n are equal to R '_at, R '_b, R "_g, R "_g, R "_h, R "_h, R ", R '", R', R '₂, R '₃, R '₄T_b, M 'and n', respectively.

p0148Examples of fluorescent dyes of the invention, mention may be made of the following dyes:

p0149<img id="imgf000023_0001" he="22" wi="135" file="imgf000023_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> 2an^"

p0150<img id="imgf000024_0001" he="16" wi="93" file="imgf000024_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0151<img id="imgf000024_0002" he="15" wi="93" file="imgf000024_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0152<img id="imgf000024_0003" he="16" wi="91" file="imgf000024_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0153<img id="imgf000024_0004" he="15" wi="95" file="imgf000024_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0154<img id="imgf000024_0005" he="17" wi="108" file="imgf000024_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0155<img id="imgf000024_0006" he="29" wi="115" file="imgf000024_0006.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p01568

p0157<img id="imgf000024_0007" he="22" wi="98" file="imgf000024_0007.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000025_0001" he="206" wi="154" file="imgf000025_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000026_0001" he="218" wi="153" file="imgf000026_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000027_0001" he="208" wi="153" file="imgf000027_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0158<img id="imgf000028_0001" he="218" wi="154" file="imgf000028_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0159<img id="imgf000029_0001" he="224" wi="153" file="imgf000029_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000030_0001" he="15" wi="134" file="imgf000030_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p016065

p0161<img id="imgf000030_0002" he="15" wi="134" file="imgf000030_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p016266

p0163<img id="imgf000030_0003" he="23" wi="138" file="imgf000030_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p016467

p0165<img id="imgf000030_0004" he="15" wi="146" file="imgf000030_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p016668

p0167<img id="imgf000030_0005" he="15" wi="143" file="imgf000030_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p016869

p0169<img id="imgf000030_0006" he="22" wi="49" file="imgf000030_0006.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p017070

p0171<img id="imgf000030_0007" he="14" wi="146" file="imgf000030_0007.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p017271 <img id="imgf000031_0001" he="215" wi="153" file="imgf000031_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000032_0001" he="27" wi="62" file="imgf000032_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p017378

p0174<img id="imgf000032_0002" he="27" wi="62" file="imgf000032_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p017579

p0176<img id="imgf000032_0003" he="16" wi="98" file="imgf000032_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p017780

p0178<img id="imgf000032_0004" he="16" wi="106" file="imgf000032_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p017982

p0180<img id="imgf000032_0005" he="16" wi="121" file="imgf000032_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p018183

p0182<img id="imgf000032_0006" he="15" wi="102" file="imgf000032_0006.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p018384

p0184<img id="imgf000032_0007" he="16" wi="109" file="imgf000032_0007.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p018585 <img id="imgf000033_0001" he="16" wi="121" file="imgf000033_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p018686

p0187<img id="imgf000033_0002" he="16" wi="101" file="imgf000033_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p018887

p0189<img id="imgf000033_0003" he="16" wi="101" file="imgf000033_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p019088

p0191<img id="imgf000033_0004" he="17" wi="116" file="imgf000033_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p019289

p0193<img id="imgf000033_0005" he="16" wi="100" file="imgf000033_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p019490

p0195<img id="imgf000033_0006" he="16" wi="107" file="imgf000033_0006.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p019691

p0197<img id="imgf000033_0007" he="17" wi="114" file="imgf000033_0007.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p019892 <img id="imgf000034_0001" he="30" wi="98" file="imgf000034_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p019993

p0200<img id="imgf000034_0002" he="30" wi="103" file="imgf000034_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p020194

p0202<img id="imgf000034_0003" he="30" wi="117" file="imgf000034_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p020395

p0204<img id="imgf000034_0004" he="30" wi="110" file="imgf000034_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p020596

p0206<img id="imgf000034_0005" he="30" wi="115" file="imgf000034_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p020797 <img id="imgf000035_0001" he="30" wi="130" file="imgf000035_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p020898

p0209<img id="imgf000035_0002" he="30" wi="117" file="imgf000035_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p021099

p0211<img id="imgf000035_0003" he="30" wi="114" file="imgf000035_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0212100

p0213<img id="imgf000035_0004" he="15" wi="105" file="imgf000035_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0214101

p0215<img id="imgf000035_0005" he="23" wi="104" file="imgf000035_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0216102

p0217<img id="imgf000035_0006" he="21" wi="95" file="imgf000035_0006.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0218103 <img id="imgf000036_0001" he="30" wi="98" file="imgf000036_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0219104

p0220<img id="imgf000036_0002" he="30" wi="103" file="imgf000036_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0221105

p0222<img id="imgf000036_0003" he="30" wi="117" file="imgf000036_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0223106

p0224<img id="imgf000036_0004" he="30" wi="110" file="imgf000036_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0225107

p0226<img id="imgf000036_0005" he="30" wi="115" file="imgf000036_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0227108 <img id="imgf000037_0001" he="30" wi="130" file="imgf000037_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0228109

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p0263<img id="imgf000039_0007" he="26" wi="66" file="imgf000039_0007.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

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p0271132

2M '

p0273133

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p0283<img id="imgf000041_0004" he="30" wi="90" file="imgf000041_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0284139

p0285<img id="imgf000041_0005" he="30" wi="92" file="imgf000041_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0286140

p0287<img id="imgf000041_0006" he="30" wi="90" file="imgf000041_0006.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0288141 <img id="imgf000042_0001" he="217" wi="153" file="imgf000042_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000043_0001" he="41" wi="154" file="imgf000043_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /> ith Year^"And M ', identical or different, representing an anionic against ion; and M⁺ representing an alkali metal.

p0289with An^", M ', identical or different, represent a cons-anionic ion such as halides, such as chloride or bromide; nitrates; sulfonates including the Ci-C₆ alkylsulphonates: Alk-S (O)₂O^" such as methyl sulfonate or mesylate and ethyl sulfonate; arylsulfonates: Ar-S (O)₂O^" such as benzenesulfonate and toluenesulfonate or tosylate; citrate; succinate; tartrate; lactate; sulphates: Alk-OS (O)^" such as methyl sulfate and ethyl sulfate; arylsulfates: Ar-OS (O)^" such as benzenesulfate and toluenesulfate; the alcoxysulfates: Alk-OS (O)₂O^" such as methoxy sulphate and ethoxy; aryloxysulfates the Ar-OS (O)₂O^", Phosphate; acetate; triflate; and borates such as tetrafluoroborate.

p0290The protected thiol dyes of formula (M ') can be synthesized in two stages. The first stage of preparing the non-thiol dye (II') according to the methods known to skilled in the art such as "Thiols and organic Sulfides "," Thiocyanates and isothiocyanates, organic, "Ullmann's Encyclopedia, Wiley-VCH, Weinheim, 2005. And the second step of protecting the thiol function according to conventional methods known in the art to give the protected thiol dyes of formula (M "). For example, to protect the thiol function -SH of the thiol dye methods of structures can be used "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed, NY, 1981, pp.193-217. "Protecting Groups" P. Kocienski, Thieme, 3^èmΘ ed., 2005, c. 5.

p0291We demonstrate this method by the method comprising i) generating thiol fluorescent dyes by reduction of a fluorescent dye in two chromophores bearing a disulfide function -SS- such as (I¹) And ii) to be protected according to conventional methods function said thiol compounds (M ') to access the protected thiol fluorescent dyes of formula (M "): <img id="imgf000044_0001" he="35" wi="143" file="imgf000044_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0292i) Reduction 2 ( "")

p0293<img id="imgf000044_0002" he="24" wi="93" file="imgf000044_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> ith R, R₂, R₃, R₄, R_at, Rb, R₉, R '_g, Rh, R'H, R₁, R ',, Y, m, n and M are as defined above and R represents a nucleofugic leaving group, such as mesylate, tosylate, triflate or halide.

p0294Alternatively, one can react a protected thiol compound (b) with a protecting group Y as defined above, prepared according to the procedures described in references cited previously, said protected thiol compound comprising at least one nucleophilic function with an amount sufficient, preferably equimolar to a "reactive fluorescent chromophore or a compound comprising such a" reactive fluorescent chromophore (a). In other words (a) comprises a nucleofugic function to form a covalent bond Σ as may be shown diagrammatically below:

p0295<img id="imgf000044_0003" he="54" wi="131" file="imgf000044_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R_at, Rb, R₉, R '_g. ', Y, m, n and M', Rh, R'H, R, R are as defined above; Nu representing a nucleophilic amine group or heterocycloalkyl, heteroaryl; % Represents a nucleofugic group such as mesylate, tosylate, triflate or halide such as bromine, iodine or chlorine. Σ represents a radical selected from -N (R) -, -N⁺(R) (R⁰) - With R and R ° as hereinbefore defined, heterocycloalkyl and heteroaryl, cationic or non.

p0296Use may also be a thiol reagent Y-SH comprising a Y moiety, the nucleophilic SH group can react on the carbon atom alpha to the halogen carried by the fluorescent chromophore atom (ET) to yield the thiol fluorescent dye protected of formula (II):

p0297<img id="imgf000045_0001" he="30" wi="128" file="imgf000045_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R_at, Rb, R₉, R '_g, Rh, R'H, R, R ', T₃, Y, m, n and M 'are as defined above, and Hal representing a halogen atom nucleofugic such as bromine, iodine or chlorine.

p0298We can also use a thioacid (oQ (e.g. thioacetic acid) which will act on halide carried by the fluorescent chromophore (a '):

p0299<img id="imgf000045_0002" he="53" wi="128" file="imgf000045_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R_at, R_b, R₉, R '_g, Rh, R'H, R, R ', rn, n, Hal, M' are as defined above and R 'represents a (dC₆) Alkyl.

p0300More particularly may be substituted by a nucleofugic leaving group a thiourea group (S = C (NRR) NRR) for generating the isothiouroniums. For example, if the thiourea group is a thioimidazolinium (β), the reaction scheme is as follows: <img id="imgf000046_0001" he="56" wi="141" file="imgf000046_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R_at, R_b, R '_c, R'd_> rg_> R '_g> Rh, R'H, R, R ,, m, n, Hal, An^" and M 'are as defined above.

p0301An alternative is to use instead of the halide comprising the fluorescent chromophore [EQ a chromophore comprising another type nucleofuge as tosylate, mesylate.

p0302According to another variant it is possible to generate an imidazoline intermediate from the halide comprising the fluorescent chromophore (Iq and a thioimidazoline (bj) to yield, after alkylation with an R-Gp with R representing an alkyl group and Gp a leaving group such as halogen such as chlorine, bromine, iodine, or a mesylate or tosylate group.

p0303<img id="imgf000047_0001" he="116" wi="138" file="imgf000047_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0304May also be substituted by a nucleofugic leaving group thiosulfate salts (eg sodium thiosulfate or potassium) to generate the Bunte salts (-SSO₃^", N / A⁺or K⁺):

p0305<img id="imgf000047_0002" he="34" wi="155" file="imgf000047_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R_at, R_b, R₉, R '_g, R_h, R '_h, R₁R ',, m, n, Hal, M' are as defined above and M⁺ representing an alkali metal such as sodium or potassium.

p0306According to another possibility, certain protected thiol fluorescent dyes (M ") can be obtained by reacting a thiol compound with a compound carrying a nucleofugic function [CQ reacted with a fluorescent chromophore carrying a nucleophilic function (hereinafter , primary or secondary amine-type, heterocycloalkyl, or heteroaryl: <img id="imgf000048_0001" he="27" wi="139" file="imgf000048_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R_at. R₅, R₉, R '_g, R_h, R '_h, R, R ', T_at, Y, m, n, M ', and Nu% (M ") as defined above.

p0307According to another possibility, the protected thiol fluorescent dyes of formula (II) may be obtained by reaction of a compound comprising a thiol group protected by a group Y, and a hydroxy group activated in advance nucleofugic leaving group (Cf), as for instance mesylate, tosylate, triflate or halide with a fluorescent chromophore (CJ) bearing a nucleophilic functional primary amine when R_b represents a hydrogen atom, or secondary amine.

p0308<img id="imgf000048_0002" he="27" wi="135" file="imgf000048_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0309with R₁, R₂, R₃, R₄, R_at, Rb, R₉, R 'g, Rh, R'H, R, R', T_at, Y, m, n, M 'and &lt;E are as defined above.

p0310By way of example a compound containing a protected thiol group, contains a nucleofugic leaving group R such as mesylate, tosylate, or triflate can undergo nucleophilic attack of the amine carried by the fluorescent chromophore styryl:

p0311<img id="imgf000048_0003" he="31" wi="158" file="imgf000048_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0312Another alternative arises from the use of halides as nucleofugic leaving group of a thiol compound which may be substituted by a primary amine function, for example carried by a fluorescent chromophore styryl: <img id="imgf000049_0001" he="27" wi="147" file="imgf000049_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0313According to another possibility, the thiol fluorescent dyes of formula (II) according to the invention can be obtained by reacting a compound having a protected thiol group and an electrophilic group Jf) with a compound comprising a nucleophilic group. For example, one can condense an aldehyde or ketone when G represents an oxygen atom with an "activated methylene" such as alkylpyridinium (§} for generating an ethylene bond> C = C <. This reaction is commonly . called condensation "Knoevenagel" by "activated methylenes" it implies those mentioned for example in patent DE19951134 particularly there may be mentioned 1, 2-dialkylpyridinium and in particular the 1, 2-dimethylpyridinium:

Y

p0315<img id="imgf000049_0002" he="58" wi="141" file="imgf000049_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R_at, R_b, R₉, R '_g, R_not, R '_h, R ', T_at, Y, m, n, M 'as defined above and G is oxygen, sulfur or a group N (R) with R representing a hydrogen atom or a (dC₄) Alkyl.

p0316Another variant of this reaction scheme is to achieve the coupling reaction of "Knoevenagel" ie subsequently from the intermediate {f]_> E amino group NR'R "may react with a reactive equivalent GP (CR₃R₄) -gp To yield (O Which itself can react with a thiol derivative Y'SH to give the aldehyde intermediate [Q. This intermediate can undergo condensation reaction "Knoevenagel" with alkylpyridinium (e) to yield the fluorescent dye thiol naphthyl (M "). <img id="imgf000050_0001" he="207" wi="151" file="imgf000050_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R ', R ", R₁, R₂, R₃, R₄, Ra, Rb, R₉, R '_g, Rh, R'H, R, m, n, Y ', and M' as defined, Gp represents a leaving group such as halogen especially Br, I, or tosylate, mesylate, triflate, and GP represents the anionic ion against straight from the leaving group Gp.

p0317Reference may be made to the book Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4^èmΘ Ed, John Willey &amp; Sons, 1992, or TW Greene "Protective Groups in Organic Synthesis" for more details on the operating conditions used in the processes mentioned above.

p0318The thiol fluorescent dyes formed can be converted into protected thiol fluorescent dyes -SY 'by the -SH thiol protection using standard protecting groups. The thiol fluorescent dyes can also beings I es metal using conventional methods known in the art such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4^èmΘ Ed, John Willey &amp; Sons, NY, 1992.

p0319The protected thiol dyes can be deprotected by conventional routes such as those described in the books "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed, NY., 1981; "Protecting Groups" P. Kocienski, Thieme, 3^èmΘ ed., 2005.

p0320Departures reagents are commercially available or accessible by conventional routes known to the skilled person. For example to synthesize the fluorescent dye chromophores two phenyl / naphthyl, bearing a disulfide function -S- S- (I¹), Can be from a reactant naphthyl difunctionalized {k}, comprising in position 2 a nucleofugic group G'-R with R representing a group (dC₄) Alkyl, mesylate, tosylate, or triflate and G 'represents an oxygen or sulfur atom or a group N (R) with R representing a hydrogen atom or a (d- C₄) Alkyl and in position 6 comprising an electrophilic group or aldehyde thioaldéyde. Two equivalents of this reagent may react with the diamine-dialkyl disulfide (Q to yield, after condensing dialdehyde / thioaldehyde disulfide (m) can be condensed with two equivalents alkylpyridinium (e) to form the compound (T). <img id="imgf000052_0001" he="84" wi="151" file="imgf000052_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> n can refer to the book Advanced Organic Chemistry, J. March, 4^èmΘ Ed, John Willey &amp; Sons, 1992, or TW Greene "Protective Groups in Organic Synthesis" for more details on the operating conditions used in the processes mentioned above.

p0321The unsymmetrical disulfide dyes of formula (I) can be synthesized in one step by reacting a thiol fluorescent dye unprotected with a protected thiol fluorescent dye to form the disulphide dye of formula (I) disymétrique.

p0322<img id="imgf000052_0002" he="60" wi="150" file="imgf000052_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R_at, R'a, Rb, R'b> R₁ R 'g> R g> R g> Rh, R h, R h, R h, R i. He h R R R R i, R2,

p0323R '₂, R₃, R '₃, R₄, R '₄, M, m ', n, n', T_atT_bAnd M 'are as defined above; Y 'represents a protective group of thiol.

p0324The composition of the invention contains at least one fluorescent dye of formula (I) or (II). Furthermore the presence of at least one fluorescent dye of formula (I) or (II), the composition of the invention may also ∞ntenir a reducing agent. This reducing agent may be chosen from thiols such as cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulphite, sulphites, thioglycolic acid and its esters, in particular glycerol monothioglycolate, and thioglycerol. This reducing agent may also be selected from borohydrides and derivatives thereof, such as salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxy borohydride of: sodium, lithium, potassium, calcium, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra n-butylammonium bromide, benzyltriethylammonium chloride); catechol borane.

p0325The dye composition according to the invention generally contains a quantity of fluorescent dyes of formula (I) or (II) of between 0.001 and 50% based on the total weight of the composition. Preferably, this amount is between 0.005 and 20% by weight and even more preferably between 0.01 and 5% by weight relative to the total weight of the composition.

p0326The dye composition may also contain additional direct dyes. These direct dyes are chosen, for example nitrobenzene direct dyes, neutral, acidic or cationic neutral azo direct dyes, acid or cationic tetraazapentamethine dyes, quinone dyes and in particular anthraquinone, acidic or cationic, direct dyes, azine , triarylmethane direct dyes, direct dyes indoamine and natural direct dyes.

p0327Among the natural direct dyes include lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin. One can also use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

p0328The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

p0329Among the oxidation bases, mention may be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols, heterocyclic bases and their addition salts.

p0330Among these couplers, mention may be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

p0331The coupler or couplers are each present in an amount between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

p0332The oxidation of bases present in the dye composition can be present in an amount ranging from 0.001 to 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6% by weight.

p0333In general, the addition salts of the oxidation bases and couplers used in the context of the invention are chosen from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts with a base, such as hydroxides of alkali metal such as sodium, potassium, ammonia, amines or alkanolamines.

p0334The medium suitable for dyeing, also called dye support, is a cosmetic medium consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned are lower alcohols -C₄, Such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, monomethyl ether of propylene glycol, monoethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

p0335The solvents when present are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight.

p0336The dye composition may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants, anionic, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and especially associative thickeners anionic, cationic, nonionic and amphoteric surfactants, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile silicones, modified or not, such as amino silicones, film-forming agents, ceramides, preserving agents, opacifiers, conductive polymers.

p0337The above adjuvants are generally present in an amount for each ranging from 0.01 to 20% by weight relative to the weight of the composition.

p0338Of course, the man of the art care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the dye composition according to the invention are not, or not substantially, impaired by the additions envisaged.

p0339The pH of the dye composition is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value using acidifying or alkalizing agents usually used for dyeing keratin fibers, or alternatively using standard buffer systems.

p0340Among the acidifying agents, mention may, for example, the inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulphonic acids.

p0341Among the alkalizing agents include, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium or potassium hydroxides and compounds formula (γ) below:

p0342NW_at-NOT

p0343R_at4 ^Ra3 (_γ) Wherein W_at is a propylene residue optionally substituted with a hydroxyl group or an alkyl radical C₁-C₄ ; R_a1, R_a2, R_a3 and R_a4, Identical or different, represent a hydrogen atom, an alkyl radical C_rC₄ hydroxyalkyl or -C₄.

p0344The dye composition may be in various forms, such as in liquid, cream, gel, or in any other form suitable for dyeing keratin fibers, especially the hair.

p0345The inventive dyeing process consists in applying the composition of the invention to keratin materials. in particular keratin fibers, especially human such as the hair, especially dark hair, the dyeing composition of the invention comprising at least one fluorescent dye of formula (I) or (II).

p0346According to a particular embodiment in the method of the 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).

p0347This reducing agent may be chosen from thiols such as cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulphite, sulphites, thioglycolic acid and its esters, in particular glycerol monothioglycolate, and thioglycerol. This reducing agent may also be selected from borohydrides and derivatives thereof, such as salts of borohydride, cyanoborohydride, triacetoxyborohydride of trimethoxyborohydride: sodium, lithium, potassium, calcium salts, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra-n butylammonium, benzyltriethylammonium); catecholborane.

p0348This pretreatment may be of short duration, in particular 0.1 second to 30 minutes, preferably 1 minute to 15 minutes with a reducing agent as mentioned previously.

p0349According to another method, 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.

p0350When the fluorescent dye is of formula (II) comprises a protecting group Y of the thiol function, the method of the invention may be preceded by a deprotection step aimed at restoring in-situ the SH function.

p0351For example it is possible to deprotect the SY function Y protecting group by adjusting the pH as follows:

p0352<img id="imgf000056_0001" he="43" wi="152" file="imgf000056_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0353<img id="imgf000057_0001" he="57" wi="152" file="imgf000057_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

p0354The deprotection step can also be performed in the heart of a hair pretreatment step as for example, the reducing pretreatment of the hair.

p0355According 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.

p0356Alternatively, 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.

p0357In the dyeing process another alternative is to apply the fluorescent dye of formula (I) or (II) together with the gearbox.

p0358According to another variant, the reducing agent is applied by post-treatment, after application of the composition containing at least one fluorescent dye of formula (I) or (II). The duration of post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably 1 minute to 15 minutes, with a reducing agent as described above. In a particular embodiment the reducing agent is a thiol agent or borohydride as described above.

p0359A particular embodiment of the invention relates to a method wherein the fluorescent dye of formula (I) or (II) may be applied directly to the hair without reducing agents, free of reducing pretreatment or reducing aftertreatment.

p0360Treatment with an oxidizing agent may optionally be combined. We can use any type of conventional oxidizing agent in the field. Thus, it can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes among which may be mentioned peroxidases, oxidoreductases with 2 electrons such as uricases and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.

p0361This oxidizing agent may be applied to the fibers before or after applying the composition containing at least one fluorescent dye of formula (I) or (II).

p0362The application of the dye composition according to the invention is generally carried out at room temperature. It may however be carried out at temperatures ranging from 20 to 180⁰C.

p0363The invention also relates to a multi-compartment device or "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 a reducing agent capable of reducing the disulfide functions of keratin materials and / or disulphide function of the dye of formula (I).

p0364One of these compartments may also contain one or more other dyes direct dye or oxidation dye.

p0365It 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); a second compartment contains a reducing agent capable of reducing the disulfide bond of keratin materials and / or disulphide function of the dye of formula (I); a third compartment contains an oxidizing agent.

p0366Another variant relates to a device with several compartment or "kit" for dyeing comprising a first compartment containing a composition with at least one protected fluorescent dye of formula (II) and a second compartment comprising a composition containing a deprotecting agent such that a base.

p0367Each of the devices mentioned above may be equipped with a means for applying to the hair the desired mixture, for example such as the devices described in patent FR 2 586 913.

p0368The following examples serve to illustrate the invention without being limiting in nature. The thiol fluorescent dyes of the examples below were fully characterized by spectroscopic and spectrometric methods conventional. EXAMPLES

SYNTHESIS EXAMPLES

p0370Example 1: Synthesis of 1-methyl-4 - {(E) -2- [4- (methyl {2 - [(1-methyl-1H-imidazol-2-yl) sulfanyl] ethyl} amino) phenyl ] vinyl} pyridinium [1]

p0371<img id="imgf000059_0001" he="16" wi="66" file="imgf000059_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0372Synthetic scheme:

p0373<img id="imgf000059_0002" he="14" wi="9" file="imgf000059_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> op ^{^}o '^s~ O 'CH₂THIS₂

p0374<img id="imgf000059_0003" he="91" wi="65" file="imgf000059_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0375Procedure:

p0376Steps 1 and 2: Synthesis of methyl sulfate 4 - ((E) -2- {4 - [(2-chloroethyl) -

p0377(Methyl) amino] phenyl} vinyl) -1-methylpyridinium

p03784.99 g 4-picoline diluted in 25 m L of dichloromethane (CH₂Cb) are stirred and heated at 40⁰C. 5 mL of dimethyl sulfate diluted in 20 mL of CH₂THIS₂ are added dropwise to the reaction medium. The mixture is maintained at 42,⁰C for 30 min after the addition, then 20 mL of isopropanol are added.

p03791.87 g of pyrrolidine diluted in 30 m L of isopropanol are added. The mixture is stirred and heated to 60⁰C for 5 min. 10.5 g of 4 - [(2-chloroethyl) (methyl) - amino] benzaldehyde was added. The mixture is stirred for 2 h at 52,⁰C and then at room temperature for 48 h. The reaction mixture is diluted in 50 mL of ethanol and stored at -25, ° C for 12 h. The precipitate obtained is filtered off at room temperature, washed with 100 mL of acetone, 3 times with 100 ml of ethyl ether and dried under vacuum in presence of P₂O₅.

p038015.1 g of orange crystals are recovered. The analyzes indicate that the product complies.

p0381Step 3: Synthesis of 1-methyl-4 - {(E) -2- [4- (methyl {2 - [(1-methyl-1H- imidazol-2-yl) sulfanyl] ethyl} amino) phenyl] vinyl} pyridinium [1] 5 g of methyl sulfate 4 - ((E) -2- {4 - [(2-chloroethyl) (methyl) amino] phenyl} vinyl) methylpyridinium iodide, 2.15 g of 2-mercapto 1-methylimidazole and 20 ml of ethanol (EtOH) were stirred and heated to 70 ⁰C for 48 h. 2.15 g of 2-mercapto-1-methylimidazole diluted in 3 mL of EtOH are added to the reaction mixture, the mixture is kept stirred at 72 ° C for 72 h. 20 mL of isopropanol and 2 ml of water are added to the reaction mixture cooled to -10⁰C. The oil is separated from the supernatant, washed with ethyl acetate (EtOAc), then dissolved in 100 mL of ethanol and stored at - 25 ° C for 48 h.

p0382The crystals obtained are filtered, washed with 20 ml of ethanol, 3 times with 100 ml of EtOAc, then dried under vacuum in presence of P₂O₅. 5.79 g of brown powder are recovered. The analyzes indicate that the product complies. NMR¹ (400 MHz, ppm, DMSO-egg₆) 2.96 (s, 3H), 3.51 (t, 2H), 3.67 (s, 3H), 3.68 (t, 2H), 4.20 (s, 3H), 6.75 (d, 2H), 7.20 ( d, 1H), 7.57 (d 2H), 7.72 (, 1H), 7.76 (d, 1H), 7.91 (d, 1H), 8.07 (d, 2H), 8.73 (d, 2H ). Example 2: Synthesis of methyl sulfate / chloride, 4 - ((E) -2- {4 - [{2 - [(1, 3- dimethyl-1H-imidazol-3-ium-2-yl) sulfanyl] ethyl } (methyl) amino] phenyl} vinyl) -1-methylpyridinium [2]

p0383<img id="imgf000061_0001" he="19" wi="64" file="imgf000061_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0384Synthetic Scheme

p0385<img id="imgf000061_0002" he="19" wi="54" file="imgf000061_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0386[1]

p0387<img id="imgf000061_0003" he="41" wi="54" file="imgf000061_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0388procedure

p0389A 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) were stirred at 70⁰C for 20 min. 500 .mu.l of dimethyl sulphate are added to the mixture. The stirring and heating are maintained for 1 h 30. 500 mg of sodium acetate are added. After 4 hours, 1 mL of dimethyl sulphate are added and stirring is continued for 15 hours at room temperature. 50 ml of acetonitrile are added. The precipitate is filtered. 100 ml of acetone are introduced into the filtrate, the oil thus obtained is washed with 3 times 100 ml of acetone and then resolubilized in 50 ml of isopropanol and stored at -25 ° C for 48 h. The precipitate formed is filtered, washed with 10 mL of iPrOH, with 3 times 20 mL of ethyl acetate then dried under vacuum in presence of P₂O₅. 1.11 g of brown powder are recovered. The analyzes indicate that the product conforms in the form of mixed salts of chloride and methyl sulfate. NMR¹ H (400 MHz, ppm, MeOH-d6) 3.06 (s, 3H), 3.35 (t, 2H), 6.68 (s, 5.44 H, methylsulfate), 3.77 (t, 2H), 3.79 (t, 6H), 4.24 (s, 3H), 6.82 (d, 2H), 7.15 (d, 1H), 7.64 (d, 2H) , 7.75 (s, 2H), 7.83 (d, 1H), 8.00 (d, 2H), 8.55 (d, 2H).

p0390Example 3: Synthesis of dichloride of 2,2 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylpyridinium) [ 3]

p0391<img id="imgf000062_0001" he="15" wi="86" file="imgf000062_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0392[3]

p0393Synthetic scheme:

p0394<img id="imgf000062_0002" he="9" wi="47" file="imgf000062_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0395<img id="imgf000062_0003" he="49" wi="86" file="imgf000062_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0396[3]

p0397Procedure:

p0398Step 1: 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino)]} dibenzaldehyde 82.3 g of phosphorus oxychloride are added to 500 mL of DMF at 0 ⁰C. After 30 min stirring at 0 ⁰A solution of 47 g of Λ /, Λ / '- (disulfanediyldiéthane-2,1-diyl) bis (N-methylaniline) was added drop by drop. The mixture was stirred 90 min. 0⁰C and 75 min. 10⁰C and 105 min. 40⁰C. It is then poured onto 2.5 L of ice water, 700 mL of 5N sodium hydroxide are added. The yellow precipitate obtained is filtered on celite, dissolved in 200 m l of dichloromethane and the solution obtained is washed with 200 m l of aqueous saturated solution of sodium chloride. After drying over magnesium sulfate and evaporation of the dichloromethane, the yellow residue (80 g) was purified by chromatography on silica gel. After drying, a light yellow powder is collected. The analyzes indicate that the product conforms to the expected structure.

p0399Step 2: dichloride of 2,2 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1- phenylene (E) ethene 2,1-diyl]} bis (1 -méthylpyridinium) [3]

p040025 g of 4,4^l- Disulfanediylbis {[ethane-2,1-diyl (methylimino)]} dibenzaldehyde and 18.5 g of N-méthylpicolinium are dissolved in 300 mL of methanol. 12.7 mL of piperidine are added to the mixture. The whole is heated with stirring at 55 ° C for 11 h. Methanol is removed in vacuo at 40⁰C. The solid is mixed with 300 m l of isopropanol. After a further drying by evaporation are introduced 200 ml of isopropanol. The mixture solidifies, it is extended by adding 100 mL of iospropanol and drained on sintered glass. The collected solid is washed with isopropanol then acetone, then dried under vacuum. After drying, 36,7g orange powder is collected. By recrystallisation from isopropanol, 27 g of purity of red orange powder are recovered. The analyzes indicate that the product conforms to the compound [3] and pure.

p0401NMR ¹H (400 MHz, MeOH-O₄) 2.99 (t, 4H), 3.81 (t, 4H), 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).

p0402Example 4: diméthoxysulfate Synthesis of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylpyridinium) [ 4]

p0403<img id="imgf000064_0001" he="30" wi="91" file="imgf000064_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0404[4]

p0405Synthetic scheme:

p0406<img id="imgf000064_0002" he="30" wi="39" file="imgf000064_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> o; , ° -

p0407-O O *%

p0408<img id="imgf000064_0003" he="49" wi="108" file="imgf000064_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0409[4]

p0410Procedure:

p0411Diméthoxysulfate 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1- phenylene (E) ethene 2,1-diyl]} bis (1 -méthylpyridinium) [4]

p04122.62 g of 4-picoline are diluted in 25 mL of dichloromethane, 3 ml of dimethyl sulfate are added to the solution, the temperature rose to reflux (40 ⁰C). After 40 min. of stirring, 50 mL of isopropanol are added, and the mixture is concentrated by distilling off the dichloromethane (mixture heated at 60⁰C). 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 h at 65⁰C, the reaction mixture is cooled to room temperature, the precipitate formed is filtered, washed with 3 times 100 m L of isopropanol. The red paste obtained is dispersed in 200 ml of isopropanol, the mixture thus obtained is refluxed and then cooled. The formed red precipitate is filtered and dried. 8.94 g of red powder are recovered. The analyzes indicate that the product conforms to the structure [4] and pure. NMR¹ H (400 MHz, DMSO-Of₆) 2.96 (t, 4H), 3.02 (s, 6H), 3.36 (s, 6H), 3.72 (t, 4H), 4.16 (s, 6H), 6.81 (d, 4H), 7.15 (d, 2H), 7.57 (d, 4H), 7.87 (d, 2H), 8.02 (d, 4H), 8.66 (d, 4H).

p0413Example 5: Synthesis of dichloride of 2,2 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene- (E) ethene-2,1-diyl]} bis (1-ethylpyridinium) [5]

p0414<img id="imgf000065_0001" he="21" wi="82" file="imgf000065_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0415[5]

p0416Synthetic scheme:

p0417<img id="imgf000065_0002" he="49" wi="82" file="imgf000065_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p04182 Cl

p0419[5]

p0420Procedure:

p0421Synthesis of dichloride of 2,2 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) - 4,1-phenylene- (E) ethene-2,1-diyl]} bis (1-ethyl pyridinium) [5] 10 g of 4,4^l- Disulfanediylbis {[ethane-2,1-diyl (methylimino)]} dibenzaldehyde and 8,1 g of N-éthylpicolinium are dissolved in 100 m L of isopropanol. 1.3 g of piperidine are added to the mixture. The whole is heated with stirring at reflux for 5 h. The isopropanol was removed under vacuum at 50⁰C. The resulting gum was triturated with acetone. 18 g of solid are collected and treated 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 are recovered. The analyzes indicate that the product conforms to the structure of the dye [5] and pure. NMR¹H (400 MHz, MeOH-Of₄) 1.57 (t, 6H), 2.98 (t, 4H), 3.11 (s, 6H), 3.8 (t, 4H), 4.73 (q, 4H), 6.85 (m, 4H), 7.23 (d, 2H), 7.69 (m, 6H), 7.85 (d, 2H), 8.29 (m, 2H), 8.38 (m, 2H), 8.67 (m, 2H).

p0422Example 6: Synthesis of di bromide 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-ethylpyridinium) [6]

p0423<img id="imgf000066_0001" he="35" wi="90" file="imgf000066_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0424[6]

p0425Synthetic Scheme

p0426<img id="imgf000066_0002" he="16" wi="63" file="imgf000066_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0427- ^~\ Br \ / iPrOH

p0428<img id="imgf000066_0003" he="35" wi="89" file="imgf000066_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0429[6] procedure

p0430Dibromide Synthesis of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) - 4,1-phenylene (E) ethene-2,1-diyl]} bis (1-ethyl pyridinium) [6]

p04314.1 g of 4,4^l- Disulfanediylbis {[ethane-2,1-diyl (methylimino)]} dibenzaldehyde_J 40 ml of isopropanol, 0.86 mL of pyrrolidine were heated to 75 ° C for 20 minutes. 4.26 g of bromide 1-ethyl-4-methylpyridinium are added to the reaction mixture, stirred and heated for 5 h. 200 m l of acetone are 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 complies and pure. NMR¹ H (400 MHz, DMSO-Of₆) 1.5 (t, 6H), 2.98 (t, 4H), 3.04 (s, 6H), 3.74 (t, 4H), 4.46 (q, 4H), 6.84 (d, 4H), 7.19 (d, 2H), 7.61 (d, 4H), 7.93 (d, 2H), 8.08 (d, 4H), 8.82 (d, 4H),

p0432Example 7: Synthesis of di bromide 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis [1- (2 - hydroxyethyl) pyridinium] [7]

p0433<img id="imgf000067_0001" he="32" wi="108" file="imgf000067_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0434[7]

p0435Synthetic Scheme

p0436<img id="imgf000067_0002" he="63" wi="108" file="imgf000067_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0437[7] procedure

p0438Synthesis of di bromide 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) - 4,1-phenylene (E) ethene-2,1-diyl]} bis [1- (2-hydroxyethyl) pyridinium] [7] 4.1 g of 4,4^l- Disulfanediylbis {[ethane-2,1-diyl (methylimino)]} dibenzaldehyde_J 40 ml of isopropanol, 0.86 mL of pyrrolidine were heated to 75 ⁰C for 1 h. 4.6 g of 1- (2-hydroxy-ethyl) -4-methyl pyridinium iodide are added to the reaction mixture, stirred and heated for 1h. 200 m l of acetone are introduced into the reaction mixture. The gum obtained is broken, filtered, washed 3 times with 150 ml of isopropanol and dried. 6.59 g of powder are recovered. The analyzes indicate that the product complies. NMR¹H (400 MHz, MeOH-Of₄) 2.97 (t, 4H), 3.1 (s, 6H), 3.78 (t, 4H), 3.97 (t, 4H), 4.51 (t, 4H), 6.83 (d, 4H), 7.09 (d, 2H), 7.61 (d, 4H), 7.83 (d, 2H), 7.98 (d, 4H), 8.56 (d, 4H).

p0439Example 8: Synthesis of di bromide 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-benzylpyridinium] [8]

p0440<img id="imgf000068_0001" he="52" wi="96" file="imgf000068_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0441[8]

p0442Synthetic Scheme

p0443<img id="imgf000069_0001" he="86" wi="96" file="imgf000069_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0444[8]

p0445procedure

p0446Step 1: Synthesis of dimethanesulfonate of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-benzyl-pyridinium) [ 8] 4.1 g of 4,4^l- Disulfanediylbis {[ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 40 mL isopropanol, 0.86 mL of pyrrolidine were heated to 75 ⁰C for 20 minutes. 5.85 g of bromide 1-Benzyl-4-methyl-pyridinium are added to the reaction mixture, stirred and heated for 5 h. The reaction mixture was stirred at room temperature for 17 hours. The supernatant is filtered, the resulting black solid is broken, washed with 200 mL of isopropanol, filt re and dried. 9.12 g of red powder are recovered. The analyzes indicate that the product complies. NMR¹H (400 MHz, DMSO-Of₆) 2.98 (t, 4H), 3.03 (s, 6H), 3.78 (t, 4H), 5.67 (s, 4H), 6.82 (d, 4H), 7.15 (d, 2H), 7.40 (m, 5H), 7.61 (d, 4H), 7.90 (d, 2H), 8.07 (d, 4H), 8.90 (d, 4H). Example 9: Synthesis of dimethyl 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylquinolinium [9 ]

p0447<img id="imgf000070_0001" he="40" wi="89" file="imgf000070_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0448[9]

p0449Synthetic Scheme

p0450<img id="imgf000070_0002" he="78" wi="89" file="imgf000070_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0451[9]

p0452procedure

p0453Synthesis of dimethyl 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methyl- imino) -4,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylquinolinium) [9 ] 4.1 g of 4,4^l- Disulfanediylbis {[ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 40 mL isopropanol, 0.86 mL of pyrrolidine were heated to 75 ⁰C for 20 minutes. 5.9 g of bromide 1, dimethyl-4-quinolinium are added to the reaction mixture, stirred and heated for 5 h. 200 m l of acetone are introduced into the reaction mixture. The precipitate obtained is filtered, washed with 200 ml of acetone and then dried. 8.73 g of black powder were recovered. The analyzes indicate that the product complies. LC-MS m / z 334, L max 524nm

p0454Example 10: Synthesis of dibromide 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methylimino) -4,1-phenylene (1 E) -prop-1-en-1, 2-diyl]} bis [ 1- (2-hydroxyethyl) - pyridinium] [10]

p0455<img id="imgf000071_0001" he="17" wi="108" file="imgf000071_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p04562 Br

p0457[10]

p0458Synthetic Scheme

p0459<img id="imgf000071_0002" he="16" wi="63" file="imgf000071_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

H

p0461OH r Br O 75 ° C 8h iPrOH

p0462<img id="imgf000071_0003" he="30" wi="109" file="imgf000071_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0463[10]

p0464procedure

p0465Step 1: dibromide Synthesis of 4,4 '- {disulfanediylbis [ethane-2,1-diyl (methyl- imino) -4,1-phenylene (1 E) -prop-1-en-1, 2-diyl]} bis [1- (2-hydroxyethyl) pyridinium] [10]

p04664.1 g of 4,4^l- Disulfanediylbis {[ethane-2,1-diyl (methylimino)]} dibenzaldehyde, 40 mL isopropanol, 0.86 mL of pyrrolidine were heated to 75 ⁰C for 20 minutes. 5.9 g of bromide 4-ethyl-1- (2-hydroxyethyl) pyridinium are added to the reaction mixture, stirred and heated for 5 h. 200 ml of acetone are introduced into the reaction mixture. The precipitate obtained is filtered, washed with 200 mL of acetone and then dried. 9.67 g purple powder was collected. The analyzes indicate that the product complies and pure. NMR¹H (400 MHz, MeOH-Of₄) 2.38 (s; 6H), 2.96 (t, 4H), 3.06 (s; 6H), 3.76 (t, 4H), 3.99 (t, 4H), 4.59 (t, 4H), 6.84 (d, 4H), 7.49 (d, 4H), 7.52 (s, 2H), 8.13 (d, 4H), 8.68 (d, 4H).

p0467Example 11: Synthesis of the salt of 1-ethyl-4 - ((E) -2- {4 - [(17- {4 - [(E) -2- (1-ethyl-pyridinium-4-yl) -vinyl] phenyl} -4,4,13,13-tetramethyl-8,9-dithia-17-aza-4,13- diazoniaoctadéc-1-yl) (methyl) amino] phenyl} vinyl) pyridinium [11]

p0468<img id="imgf000072_0001" he="23" wi="139" file="imgf000072_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0469[11]

p0470Synthetic Scheme

p0471HN .S_V^_/OH

HO

p0473<img id="imgf000072_0002" he="95" wi="127" file="imgf000072_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> [11]

p0474procedure

p0475Step 1: Synthesis of 4 - [[3- (dimethylamino) propyl] (methyl) amino] benzaldehyde 10 g of 4-fluorobenzaldehyde and 12 g of potassium carbonate were mixed in 20 mL of N-methylpyrrolidinone (NMP) and heated to 50 ⁰C. 13 mL of NNN'-trimethyl-1,3-propanediamine are added and the mixture was heated to 80 ⁰C for 10 h. After cooling, 100 ml of acetone are added. The resulting mixture was filtered and concentrated in vacuo. 21, 85 g of oil are recovered, which contain the expected compound and 0.7 molar equivalents of NMP.

p0476Step 2: Synthesis of dimethanesulfonate of disulfanediyldipropane-3,1-diyl 9 g of 3,3'-disulfanediyldipropan-1-ol are diluted in 50 m L of ethyl acetate. 20 g of triethylamine are added, and the mixture is cooled to 0⁰C. 14.3 g of mesyl chloride were gradually added while maintaining the temperature below 5 ⁰C. At the end of the addition, the mixture is stirred for one hour at room temperature and then poured in 100 m L of water / ice. The product is extracted by 100 m L of ethyl acetate, washed with 2 x 100 ml of molar hydrochloric acid solution, 2 x 100 mL water, 100 mL of a saturated solution of sodium hydrogencarbonate and 2 x 100 mL of saturated sodium chloride. The organic phase is dried over sodium sulfate and concentrated in vacuo. 6 g of yellowish oil are recovered; analyzes show that the product complies.

p0477Step 3: Synthesis of dimethanesulfonate of N, N '- (disulfanediyldipropane-3,1-diyl) bis {3 - [(4-formylphenyl) (methyl) amino] -N, N-dimethylpropan-1-aminium 2,2} g of 4 - [[3- (dimethylamino) propyl] (methyl) amino] benzaldehyde and 1, 7 g of dimethanesulfonate of disulfanediyldipropane-3,1-diyl are mixed in 2 mL of N-methylpyrrolidinone at 80 ⁰C for 22 h. After cooling the reaction mixture, 20 mL of ethanol are added. The solid obtained is filtered, is very hygroscopic. Purification by trituration in dichloromethane led to the isolation of 232 mg of solid accordance with the expected product.

p0478Step 4: Synthesis of the salt of 1-ethyl-4 - ((E) -2- {4 - [(17- {4 - [(E) -2- (1-ethylpyridinium-4-yl) -vinyl] -phenyl} -4,4,13,13-tetramethyl-8,9-dithia-17-aza-4,13-diazoniaoctadéc-1- yl) (methyl) amino] phenyl} vinyl) pyridinium [11]

p0479230 mg dimethane sulfonate of N, N '- (disulfanediyldipropane-3,1-diyl) bis {3 - [(4- formylphenyl) (methyl) amino] -N, N-dimethylpropan-1-aminium} and 163 mg of bromide 1-ethyl-4-methylpyridinium iodide were mixed in 5 ml of isopropanol. 53 μl_ pyrrolidine are added, the mixture is stirred at 70⁰C for 6 h and stirred at room temperature for 72 hours. After cooling the mixture to -20⁰C., the solid formed is filtered, taken up in methanol and reprecipitated by adding 200 mL of terbutylméthyléther. 118 mg of black solid is collected. The analyzes indicate that the product conforms to the expected structure (MS (ESI +): mass peak m / z = 199)

p0480Example 12: Synthesis of di bromide 2,2 '- {disulfanediylbis [ethane-2,1-diyl- imino-4,1-phenylene (E) ethene-2,1-diyl]} bis [1- (2- hydroxyethyl) pyridinium] [12]

p0481<img id="imgf000074_0001" he="23" wi="77" file="imgf000074_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0482<img id="imgf000075_0001" he="9" wi="22" file="imgf000075_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

DMSO

p048452h to 1βO ° CH, N OH

p048518C-6 10%

p0486<img id="imgf000075_0002" he="10" wi="32" file="imgf000075_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0487MSCI pyridine

p0488<img id="imgf000075_0003" he="13" wi="41" file="imgf000075_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p04891) Na₂S₂O₃

p04902) NaOH

p0491<img id="imgf000075_0004" he="48" wi="82" file="imgf000075_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0492procedure

p0493Step 1: Synthesis 4 - [(2-hydroxyethyl) amino] benzaldehyde 1, 24 g of 4-fluorobenzaldehyde, 10 mL of DMSO distilled over calcium hydride, 1, 16 g of sodium carbonate and a catalytic amount of ether 18 -crown-6 (5 mol%) are mixed with stirring for 10 minutes. 1.25 ml of ethanolamine are slowly added to the reaction mixture stirred and heated to 160⁰C for 52 h. After cooling to 75⁰C the reaction mixture is hydrolyzed with distilled water. Dilute hydrochloric acid is added to the mixture until a pH between 6 and 7 and then stirred under heating at 40 ° C for 6 h. The alcohol obtained is extracted with ethyl acetate. The organic phase is washed several times with distilled water and brine, then dried over magnesium sulfate. The mixture was concentrated in vacuo, purified by gel chromatography silice.1,2 g of brown solid are collected. Analyses show that the product is consistent with the expected structure.

p0494Step 2: Synthesis of methyl 2 - [(4-formylphenyl) amino] ethyl 0.4 g of 4 - [(2-hydroxyethyl) amino] benzaldehyde and 10 mL of pyridine are mixed under stirring. The reaction medium is cooled in a dry ice-acetone bath. A 0⁰C, 0.18 ml of mesyl chloride are added dropwise. The reaction mixture is stirred for 17 h at a temperature between 0 and 5⁰C, then ice water is included in the mixture. The solid formed is triturated and filtered, washed with distilled water and then dried in vacuo. 550 mg of white powder are collected. The analyzes indicate that the product complies.

p0495Step 3: Synthesis of 4,4 '- [disulfanediylbis (ethane-2,1-diylimino)] dibenzaldehyde 0.5 g of 2 - [(4-formylphenyl) amino] ethyl methyl sulphate, 3 mL of ethanol-water solution ( 1: 2) and 0.546 g of sodium thiosulfate are mixed with stirring at reflux for 2 h. The resulting yellow solution was cooled, then 2.8 mL of 35% sodium hydroxide is added dropwise. The mixture is stirred at 75 ° C for 1 h. After cooling, a light yellow solid is filtered, washed with water and then dried under vacuum. 237 mg of yellow powder were recovered. The analyzes indicate that the product complies and pure. NMR¹(400 MHz, CDCI₃) 2.85 (t, 4H), 3.5 (m, 4H), 4.61 (t, 2H), 63.57 (d, 2H), 7.63 (d, 4H), 9.66 (s, 2H)

p0496Step 4: Synthesis of di bromide 2,2 '- disulfanediylbis {[2,1-ethane-4,1-phenylene diylimino- (E) ethene-2,1-diyl]} bis [1- (2-hydroxyethyl) pyridinium] [12] 200 mg of 1- (2-hydroxyethyl) -2-methylpyridinium iodide and 260 mg of 4,4'- [disulfanediylbis (ethane-2,1-diylimino)] dibenzaldehyde are dispersed in 4 mL of isopropanol. 1 mL solution consisting of 666 mg of acetic acid, 790 mg of pyrrolidine and 10 ml of isopropanol is added to the suspension. The mixture is stirred for 16 h. 130 mg of bromide 1- (2-hydroxyethyl) -2-methylpyridinium bromide are added and the mixture is heated at 60 ° C for 6 h. The solid formed is filtered, triturated in 5 mL isopropanol and 0.5 mL of water and then refiltered and dried. 118 mg of black solid is collected. The analyzes indicate that the product conforms to the expected structure. NMR¹H (400 MHz, DMSOd₆) 2.96 (t, 4H), 3.46 (m, 4H), 3.84 (m, 4H), 4.8 (t, 4H), 5.22 (t, 2H), 6.70 (d, 4H), 6.80 ( t, 2H), 7.28 (d, 2H), 7.65 (d, 4H), 7.72 (dd, 2H), 7.86 (d, 2H), 8.35 (dd, 2H), 8.45 (d, 2H), 8.67 (d, 2H). Example 13: Synthesis of di methyl sulfate, 2,2 '- {disulfanediylbis [ethane-2,1-diylimino-2,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylquinolinium) [13 ]

p0497<img id="imgf000077_0001" he="25" wi="70" file="imgf000077_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0498[13]

p0499Synthetic Scheme

p0500<img id="imgf000077_0002" he="16" wi="13" file="imgf000077_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

DMSO

,OH

p0503H₂C6 N 18 -10%

p0504160 ° C

p0505<img id="imgf000077_0003" he="46" wi="43" file="imgf000077_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0506N / A₂S₂O₃

p0507<img id="imgf000077_0004" he="69" wi="78" file="imgf000077_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> [13]

p0508procedure

p0509Step 1: Synthesis of 2 - [(2-hydroxyethyl) amino] benzaldehyde 1, 24 g of 2-fluorobenzaldehyde, 10 mL of DMSO distilled over calcium hydride, 1, 16 g of sodium carbonate and a catalytic amount of ether 18-crown-6 (5 mole%) were mixed with stirring for 10 minutes. 1, 3 m L g of ethanolamine are added. After stirring at 160⁰C for 3 days, the mixture was cooled to 75 ° C and hydrolyzed with distilled water. The pH of the solution is lowered to 6 by addition of diluted hydrochloric acid kept under stirring and heating at 40⁰C for 18 h. The alcohol obtained is extracted with ethyl acetate. The organic phase is washed several times with distilled water and brine, then dried over magnesium sulfate. The mixture was concentrated in vacuo then purified by chromatography on silica gel. 1, 2 g of brown product are collected.

p0510Step 2: Synthesis of 2 - [(2-formylphenyl) amino] ethyl methanesulphonate 0.5 g of 2 - [(2-hydroxyethyl) aminojbenzaldéhyde and 10 ml of distilled pyridine are mixed under stirring at 0⁰C. 0.23 ml of mesyl chloride are added dropwise. The reaction mixture is stirred for 17 h at a temperature between 0 and 5 ° C, then ice water is included in the mixture. The white solid obtained is filtered, rinsed with distilled water and dried under vacuum (650 mg). The analyzes indicate that the product complies and pure.

p0511Step 3: Synthesis of 2,2 '- [disulfanediylbis (ethane-2,1-diylimino)] benzaldehyde di-

p05120.5 g of 2 - [(2-formylphenyl) amino] ethyl methanesulfonate and 0.546 g of sodium thiosulfate pentahydrate were heated in 3 mL of ethanol / water solution (1/2) at 90 ⁰For 15 g. The resulting solution was cooled and 2.8 mL of 35% sodium hydroxide are added and the mixture is stirred at 75 ° C for 1 h. After cooling, the yellow solid formed was filtered, washed with distilled water and dried under vacuum. 222 mg of powder are collected. Analyses show that the product conforms to the expected: 1H NMR (400 MHz, CDCl3) 2.96 (t, 4H), 3.63 (dt, 4H), 6.74 (t, 2H), 6.76 (d, 2 H), 7.41 (t, 2H), 7.50 (d, 2H), 8.54 (t, 2H), 9.84 (s, 2H). Step 4: Synthesis of dimethyl sulfate, 2,2 '- {disulfanediylbis [ethane-2,1-diylimino-2,1-phenylene (E) ethene-2,1-diyl]} bis (1-methylquinolinium) [13] 210 mg of 2,2^l- [Disulfanediylbis (ethane-2,1-diylimino)] dibenzaldehyde and 360 mg of 1, 2-diméthylquinolinium are dispersed in 4 ml of isopropanol. 1 mL of solution consisting of 790 ml of pyrrolidine, 666 mg of acetic acid and 10 mL isopropanol qs are added The mixture is stirred at room temperature for 10 days, 180 mg quinolinium are added and stirring is maintained for 3 days at room temperature. The mixture was filtered, the collected solid was dried (214 mg). The analyzes indicate that the product conforms to the expected structure. LCMS (ESI +) 320, λ_max 494 nm.

EXAMPLES OF COLOUR

p0514Example 1: color process - compound [1]

p0515A 1 g lock of hair of tone height 4 are arranged at the bottom of a bowl. 1 mL of molar solution of ammonium thioglycolate at pH 8.5 were diluted with 9 mL of water. The solution thus obtained is applied to the strands and allowed to react for

p051630 min. The locks were rinsed with tap water and then rearranged in a bowl. 10 mL of aqueous solution containing 49 mg of compound [1] are applied for 30 minutes at room temperature (the locks are turned and re-treated after

p051715 minutes).

p0518The locks were then rinsed with running water and dried.

p0519After staining, the wick of tone height 4 has become visually lighter than untreated control locks.

p0520Example 2: staining method - compound [2]

p0521A 1 g lock of hair of tone height 4 are arranged at the bottom of a bowl. 1 mL of molar solution of ammonium thioglycolate at pH 8.5 were diluted with 9 mL of water. The solution thus obtained is applied on the locks and left to act for 30 min. The locks were rinsed with tap water and then rearranged in a bowl. 10 mL [2] aqueous solution containing 63 mg of compound are applied for 30 minutes at room temperature (the locks are turned and re-treated after 15 minutes). The locks were then rinsed with running water and dried.

p0522After staining, the wick of tone height 4 has become visually lighter than untreated control locks.

p0523EXAMPLE 3 staining method - compounds [3] to [12] Preparation of a composition A

p0524Dye disulfide [3] to [12] 10^"3 mol%

p0525Benzyl Alcohol 4 g

p05266 g polyethylene glycol 6EO

p0527Hydroxyethylcellulose 0.7 g

p0528Alkylpolyglycoside in aqueous solution at 65% AS 4.5 g

p0529Demineralized water qs 100 g

p0530Preparing a composition B

p0531Thioglycolic acid 1M

p0532Sodium hydroxide qs pH 8.5

p0533Demineralized water qs 100 g

p0534At the time of use, mix compositions A (9 mL) and B (1 mL) and then apply the mixture to a lock of 1 g of dark hair (tone height 4) for 30 minutes at room temperature (the locks are turned over and reimpregnated after 15 minutes).

p0535After rinsing with running water and drying, there is a thinning of hair thus treated: the lock of tone height 4 has become visually lighter than untreated control locks.

p0536Persistence vis-à-vis successive shampooing:

p0537The locks thus treated are divided into two, one half is subjected to 5 successive shampooing according to a cycle which includes the wetting of the locks with water, washing with a conventional shampoo, rinsing with water followed by drying. visual observations

p0538When shampoos examples [1], [2], [3], [4], [5], [7], [8], [9], [10] and [12] there is no visible bleeding, the shampoo foam and the rinsing water are not colored.

p0539The observed color is preserved and the lightening effect remains visible on the height of your hair so treated 4. Results in the L^*at^*b^* :

p0540The color of the locks before and after the 5 washes was evaluated in the L * a * b * using a spectrophotometer CM 2600D MINOLTA ®, (illuminant D65). In this L * a * b *, L * represents lightness, a * indicates the color axis red / green axis and b * the blue / yellow color. The higher the value of L, the higher the color lighter or less intense. Conversely, the more the value of L is small, the color is dark or intense. Over the a * value the higher the grade is red and the b * value is high more yellow the shade.

p0541The change in coloring between the HT4 hair strands or HT4,5 stained and washed is measured by (.DELTA.E) using the following equation:

p0542Δ E = V (L^* - L₀^*f + (a^* - at₀^*f + (b^* - b₀^*f

p0543In this equation, L *, a * and b * represent the values ​​measured before dyeing, and L₀* Ao bo * and * represent the values ​​measured before coloring (or shampoo).

p0544Plus the value of .DELTA.E, the greater the difference in color between the strands or 4.5 HT4 and colored strands is important.

p0545<img id="imgf000081_0001" he="66" wi="143" file="imgf000081_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /><img id="imgf000082_0001" he="105" wi="143" file="imgf000082_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0546The results of the above table show that the color changes very little after 5 shampoos about wicks originally colored HT4 with the dyes of the invention. Thus, the coloring and the lightening effect on the hair remains virtually unchanged, showing a very good resistance to shampoos dyes of the invention.

p0547Results obtained on strands of HT4,5 treated with the compounds 3-5, followed by a series of 30 shampoos

p0548<img id="imgf000082_0002" he="57" wi="152" file="imgf000082_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

p0549The results of the above table show that the color changes very little even after 30 shampoos about wicks originally colored HT4.5 with the dyes of the invention. Thus, the coloring and the lightening effect on the hair remains virtually unchanged, showing a very good resistance to shampoos dyes of the invention.

p0550Reflectance Results:

p0551lightening effectiveness of the compositions according to the invention and their vis-a-vis remanence successive shampoos were expressed in terms of the reflectance of the hair. These reflectances are compared to the untreated reflectance of a lock of hair of tone height TH4.

p0552The reflectance is measured using a MINOLTA apparatus spectrophotocolorimeter KONIKA- ⁽S, CM 260Od and after irradiation of the hair with visible light in the wavelength range from 400 to 700 nanometers.

p0553<img id="imgf000083_0001" he="68" wi="150" file="imgf000083_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0554Reflectance of the locks treated with the compounds 3, 4 and 5 to the application and after 5 shampoos

p0555Reference Compound 3 Compound 3-5 shampoos

p0556- * - Compound 4

p0557- - -A - - Compound 4-5 shampoos - "- Compounds <img id="imgf000084_0001" he="42" wi="94" file="imgf000084_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> - - -a- - - Compound 5-5 shampoos

p05580o o (M ot o (D o (O Oo (oM to o (B (oO Oo oo No ^ (O Oilo oO ttttt in -om in -o co co co co co i ^ -

p0559Wavelength (nm)

p0560Reflectance of the locks treated with the compounds 10 and 12 to the application and after 5 shampoos

p056110

p0562Compound 10-5 shampoos <img id="imgf000084_0002" he="28" wi="9" file="imgf000084_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> 5 12- 12 shampoos <img id="imgf000084_0003" he="46" wi="112" file="imgf000084_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0563Wavelength (nm)

p0564We first note that the reflectance of a lock of hair treated with a composition according to the invention is higher than that of untreated hair. The treated locks therefore appear brighter.

p0565In addition, the results show that the reflectance of the locks of hair of tone height 4 treated with the composition of the invention change very little after 5 shampoos. Thus, the coloring and the lightening effect on the hair remains virtually unchanged, showing a very good resistance to shampoos dyes of the invention.