Dyeing composition containing a thiol/disulphide fluorescent colorant comprising a heterocycle, with an internal cationic charge, and method for lightening keratin materials using said colorant

Translation of description of equivalent WO 2007110539 A2

DYE COMPOSITION CONTAINING A FLUORESCENT DYE

THIOL / DISULPHIDE HETEROCYCLE AND INTERNAL CATIONIC CHARGE,

METHOD FOR LIGHTENING KERATIN MATERIALS FROM

EC DYE -

p0005The invention relates to the coloring of keratin materials with fluorescent dyes comprising a thiol or disulphide heterocycle.

p0006It 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.

p0007The 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 triarylmethane.

p0008The 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.

p0009Furthermore, the dyeing of keratinous fibers from conventional direct dyes does not allow to significantly lighten keratin fibers.

p0010The lightening of the color of keratin fibers, especially dark to lighter shades, by optionally modifying the shade thereof, constitutes an important demand.

p0011Conventionally, 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.

p0012This 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 fragile. Finally, the lightening or bleaching of keratin fibers with oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in hair straightening treatments. Another 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. To increase the fastness of direct colorings, 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 2024509;

p0013Furthermore 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. Other 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.

p0014Finally, WO 2005/097051 describes the document disulfide dyes aza imidazoliums for the direct dyeing of keratin fibers.

p0015The 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 fibers keratin and that do not alter their cosmetic properties.

p0016This 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 selected from the dyes of formulas (I) and (II):

p0017<img id="imgf000004_0001" he="62" wi="144" 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; formulas (I) or (II) wherein:

p0018> (Het and N- (HEF N - identical or different, represent a group

p0019_\"Vy \ ^ \ y heïerocyclique saturated or unsaturated; especially monocyclic containing 5 to 7 ring members and comprising one or two heteroatoms selected from nitrogen, oxygen or sulfur, particularly the heteroatom is an atom of nitrogen, in particular the heterocycle is selected from pyrazolyl, pyrrolidinyl, piperazinyl, homopiperazinyl, piperidinyl, morpholinyl and imidazolyl;

p0020> R₉, R 'g, R "_g, R " 'g, R_h, R'H, R "h and R" '_h, Identical or different, represent a hydrogen atom, halogen, amino, (di) (C_rC₄) Alkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, alkoxy, C₁-C₄(Poly) hydroxyalkoxy, C₂-C₄(Ci-C₄) Alkylcarbonyloxy, (C₁-C₄) Alkoxycarbonyl, (Ci-C₄) Alkylcarbonylamino, acylamino, carbamoyl, (C_rC₄) Alkylsulfonylamino, aminosulfonyl, or a (C_rC₁₆) Alkyl optionally substituted by a group selected from (Ci-C₁₂) Alkoxy, hydroxy, cyano, carboxy, amino, (di) (Ci-C₄) Alkylamino, 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 "_g, R "_g, R_h, R '_h, R "_hAnd R "_h represent a hydrogen atom or a (Ci-C₄) alkyl

p0021> Ri, R'j, R 'i and R "i are identical or different, represent a hydrogen atom or a (C_rC₄) Alkyl; particularly Rj, R'j, R 'i and R "i, represent a hydrogen atom;

p0022> R₁, R ', R₂, R '₂R3, R'3_> R₄ and R '₄, Identical or different, represent a hydrogen atom or a (C_rC₄) Alkyl, (C-ι-C₄) Alkoxy, hydroxy, cyano, carboxy, amino, (CrC₄) Alkylamino, (C₁-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; including R₁, R'-i, R₂, R '₂R3, R'3, R₄ and R '₄Are hydrogen atoms or an amino group; particularly R₁, R ', R₂, R '₂R3, R'3, R₄ and R '₄, Represent a hydrogen atom;

p0023> T₃ and T_bIdentically or differently represent: i) a σ covalent bond, ii) one or more radicals or combinations thereof selected from -SO₂-

p0024-O-, -S-, -N (R) -, -N⁺(R) (R⁰) -, -C (O) -, with R and R ° are identical or different, representing a hydrogen atom, an alkyl radical C₁-C₄Hydroxyalkyl, C₁-C₄ or aryl (-C₄) Alkyl; including T_at is identical to T_b and they represent a σ covalent bond or a group selected from -N (R) -, -C (O) - -C (O) -N (R) -, -N (R) -C (O) -, - C (O) -N (R) -C (O) -,

p0025-0-C (O) -, -C (O) -O- and -N⁺(R) (R⁰) -, With R and R ° are identical or different representing a hydrogen atom, a (Ci-C₄) Alkyl; particularly T₃ and T_b represent a σ bond; iii) a heterocycloalkyl or heteroaryl radical, cationic or noncationic, preferably monocyclic, containing two heteroatoms including, particularly two nitrogen atoms, and in particular having from 5 to 7 members such as imidazolium, piperazyl, piperazinium, homopiperazyle or optionally homopiperazinium substituted by a group (-C₄) Alkyl such as methyl;

p0026> M, m ', n and n', identical or different, represent an integer ranging from O to 6 with m + n, m '+ n', identical or different, represent an integer ranging between 1 and 10; particularly the sum m + n = m '+ n' = an integer ranging between 2 and 4; preferably m + n = m '+ n' = 2;

p0027> M 'is an anionic ion-against; and

p0028> Y is i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N⁺R⁰¹R¹³R⁷R⁵ 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 (Ci-C₄) Alkyl; or v) a protective group of thiol;

p0029it being understood 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).

p0030Another object of the invention is a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye of formula (I) or (II) as defined above, and optionally a reducing agent.

p0031The invention also relates to novel fluorescent dyes of formula (I) or (II) as defined above.

p0032The dyeing process according to the invention allows to visibly color dark keratin materials, in particular dark human keratin fibers, especially dark hair.

p0033Furthermore, 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, sweating) 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.

p0034Within the meaning of the invention, dark keratin material means the one with luminescence L * measured in the CIE L * a * b * less than or equal to 45 and preferably less than or equal to 40, given also that L^*= 0 is equivalent to black and _ * 100 = white.

p0035Within 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).

p0036The lightening of the hair is evaluated by the variation in "tone height" before and after application of the compound of formula (I) or (II).

p0037The 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 hairstyling professionals and are published in the book "Science of hair treatment"

p0038Charles Zviak 1988 Ed. Masson, p. 215 and 278.

p0039The 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.

p0040An 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.

p0041Preferably, the composition should, after application to the hair, for example chestnut, bring the results below.

p0042- We are interested in hair reflectance performance when irradiated with visible light in the wavelength range from 400 to 700 nanometers.

p0043- It then compares the reflectance curves as a function of wavelength, of hair treated with the composition of the invention and the untreated hair.

p0044- 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.

p0045- This means that, in the wavelength range 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 beach where the curve - reflectance corresponding to the treated hair is superimposable or lower than the reflectance curve corresponding to the untreated hair.

p0046Preferably, 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 from 550-620 nanometers.

p0047Within the meaning of the present invention, and unless a different indication is given: - the radicals "aryl" or "heteroaryl" or the aryl or heteroaryl part of a radical may be substituted by at least one substituent on a carbon atom, selected from:

p0048. alkyl C₁-This₆, Preferably -C₈Optionally substituted by one or more radicals chosen from hydroxyl, alkoxy, C_r C₂(Poly) hydroxyalkoxy C₂-C₄, Acylamino, amino substituted with two alkyl radicals, identical or different C_rC₄ , Optionally bearing at least one hydroxy group, or the two radicals to form, with the nitrogen atom to which they are attached, a heterocycle comprising

p00495 to 7 members, preferably 5 or 6 membered saturated or unsaturated optionally substituted optionally comprising another heteroatom identical to or different from nitrogen;

p0050• a halogen atom such as chlorine, fluorine or bromine;

p0051• a hydroxyl group;

p0052. -alkoxy -C₂ ; • alkylthio -C₂ ;

p0053. a radical (poly) hydroxyalkoxy C₂-C₄ ; . an amino radical;

p0054• a heterocycloalkyl with 5 or 6 members;

p0055• a heteroaryl radical with 5 or 6 members optionally cationic, preferably imidazolium, optionally substituted by

p0056(-C₄) Alkyl, preferably methyl;

p0057. an amino radical substituted by one or two alkyl radicals, identical or different C_rC₆ optionally bearing at least: i) a hydroxyl, ii) an amino group optionally substituted by one or two alkyl radicals C₁-C₃ optionally substituted, 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,

p0058• -NR-COR 'in which the radical R is a hydrogen atom, an alkyl radical -C₄ optionally bearing at least one hydroxyl group and the radical R 'is alkyl C₁-C₂ ; • (R)₂N-CO- in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group; . R¹SO₂-NR- Wherein 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 C₁-C₄A phenyl radical;

p0059• (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, • a carboxyl group in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted); . a cyano group;

p0060• 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;

p0061- 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:

p0062• hydroxy, • alkoxy, C₁-C₄,

p0063. (Poly) hydroxyalkoxy, C₂-C₄,

p0064• a radical alkylthio, C₁-C₂ ;

p0065• RCO-NR'- wherein the radical R 'is a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group and the radical R is an alkyl radical C₁-C₂And amino substituted with two alkyl groups are identical or different C₁-C₄ optionally bearing at least one hydroxyl group;

p0066. RCO-O- wherein the radical R is an alkyl radical C₁-C₄, Amino substituted by one or two alkyl groups are identical or different C₁-

p0067C₄ optionally bearing at least one hydroxyl group, 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 not nitrogen;

p0068. RO-CO- group wherein R is an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group;

p0069- A cyclic, heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical may also be substituted by one or more oxo or thioxo groups;

p0070- 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; - 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 selenium and of which at least one ring is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tétrazolyie, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phénooxazolyle, pyrazinyl, pyrazolyl, pyrilyle, pyrazoyltriazyle, pyridyl, pyridinoimidazolyle, pyrrolyl, quinolyl, tétrazolyie, 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; - 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, 1, 3,5 trimétylsillylphényle and adamantyl ;

p0074- A "heterocycle or 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;

p0075- An "alkyl group" is a hydrocarbon radical C₁-C₁₆Linear or branched, preferably -C₈ ;

p0076- 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 C₁-C₄, 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; v) or a quaternary ammonium group

p0077-N R'R "R '" Mr.^" wherein R ', R ", R"', identical or different, represent a hydrogen atom, or an alkyl group C₁-C₄Or else -NR¹R¹¹R " 'forms a heteroaryl such as imidazolium optionally substituted by a C₁- C₄ alkyl, and M represents the against-ion of the organic acid, mineral acid or corresponding halide, - 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-cs;

p0078- A "alkylthio" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched C₁-C₁₆ preferably C₁-C₈ ; when the alkylthio group is optionally substituted, this means that the alkyl group is optionally substituted as defined above;

p0079- 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 ;

p0080- 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) alkyl sulfates: Alk-OS (O)^" such as méthysulfate and ethylsulfate; x) arylsulfates: Ar-OS (O)^" such as benzenesulfate and toluenesulfate; xi) alcoxysulfates: Alk-OS (O)₂O^" such as methoxy sulphate and ethoxy; xii) aryloxysulfates: Ar-OS (O)₂O^"Xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

p0081Fluorescent dyes of formula (I) or (II) are compounds capable of absorbing in the LJV or visible radiation at a wavelength λ_abs understood between 250 and 800 nm and capable of réémettrent in the visible range at a transmission wavelength λ_em between 400 and 800 nm.

p0082Preferably the fluorescent compounds of the invention are dyes capable of absorbing in the visible λ_atb_S between 400 and 800 nm and re-emit in the visible λ_em between 400 and 800 nm. More preferably fluorescent dyes heterocyclic group of formula (I) or (II) are dyes capable of absorbing at a λ_atbs between 420 nm and 550 nm and re-emit in the visible range at a λ_em between 470 and 600 nm.

p0083The fluorescent compounds of formula (II) which 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.

p0084A particular embodiment relates to the thiol fluorescent dyes group of formula

p0085(II) function SY where Y is a hydrogen atom, or an alkali metal.

p0086Preferably Y is hydrogen. According to another embodiment of the invention, in formula (II) above, Y is a protecting group known in the art such as those described in the books "Protective Groups in Organic

p0087Synthesis ", TW Greene, John Willey &amp; Sons ed, NY, 1981, pp.193-217.

p0088"Protecting Groups" P. Kocienski, Thieme, 3^th ed., 2005, c. 5. Particularly when Y represents a group protecting the thiol group, Y is selected from the following radicals:

p0089• (C_rC₄) Alkylcarbonyl;

p0090• (C_rC₄) Alkylthiocarbonyl;

p0091• (Ci-C₄) Alkoxycarbonyl; ^" (C₁-C₄) Alkoxythiocarbonyl;

p0092• (Ci-C₄) Alkylthio-thiocarbonyl;

p0093• (di) (C₁-C₄) (Alkyl) aminocarbonyl;

p0094• (di) (C₁-C₄) (Alkyl) aminothiocarbonyl;

p0095• arylcarbonyl as phenylcarbonyl; • aryloxycarbonyl;

p0096• aryl (C_rC₄) Alkcoxycarbonyle;

p0097• (di) (C₁-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl;

p0098• (C_rC₄) (Alkyl) arylaminocarbonyl; • carboxyl;

p0099¹ 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 aryl such as phenyl, dibenzosuberyl, or 1, 3,5-cycloheptatrienyl,

p0101• optionally substituted heteroaryl; including the cationic or noncationic heteroaryl comprising 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,

p01021, 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 ( Cr C₄) Alkyl such as methyl, or polyhalo (C₁-C₄) Alkyl such as trifluoromethyl; iii) or tricyclic ABC:

p0103<img id="imgf000014_0001" he="16" wi="36" file="imgf000014_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein both rings A, C_ optionally comprise 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;

p0104• optionally substituted heterocycloalkyl, optionally cationic, the heterocycloalkyl group is especially 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 (CrC₄) Alkyl, oxo or thioxo; or heterocycle represents the following group:

p0105<img id="imgf000015_0001" he="29" wi="37" file="imgf000015_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein R '^c, R '^d, R '^e, R '^f, R '⁹ and R '^h, Identical or different, represent a hydrogen atom or a (Ci-C₄) Alkyl, or else two groups R '⁹ R '^hAnd / or R '^e R '^f form an oxo or thioxo, or else R '⁹ R '^e 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^" is against ion;

p0106• isothiouronium -C (NR '^cR '^d) = N⁺R '^eR '^f; Year^" R '^c, R '^d, R '^e and R '^f, Identical or different, represent a hydrogen atom or a (Ci-C₄) Alkyl; preferably, R '^c to R '^f represent a hydrogen atom; and An^" is against ion;

p0107- Isothiourea -C (NR '^cR '^d) = NR '^e; R '^c, R '^d and R '^e as defined above; • (di) aryl (-C₄) Alkyl 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, (CrC₄) Alkylcarbonyl, (di) (-C₄) (Alkyl) amino such as dimethylamino; • (di) heteroaryl (C_rC₄) Akyle 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 groups such as alkyl especially methyl, preferably (di) heteroaryl (Ci-C₄) Akyle is (di) heteroarylmethyl or (di) heteroarylethyl;

p0108"CR¹R²R³ with R¹, R² and R³ identical or different, representing a halogen atom or a group selected from:

p0109- (C₁-C₄) Alkyl;

p0110- (C₁-C₄) Alkcoxy;

p0111- Optionally substituted aryl such as phenyl optionally substituted with one or more groups such as (CrC₄) Alkyl, (-C₄) Alkcoxy, hydroxy; - Optionally substituted heteroaryl, such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted by a (C₁- C₄) Alkyl;

p0112- P (Z¹ ) R '¹ R¹²R '³ R '¹And R '² identical or different, representing a hydroxyl, (CrC₄) Alkcoxy or alkyl, R '³ represents a hydroxy group or (C₁-C₄JaIkCOXy, and Z¹ represents an atom of oxygen or sulfur;

p0113"Hindered cyclic such as adamantyl; • alkoxy (-C₄) Optionally substituted alkyl such as methoxymethyl

p0114(MOM), ethoxyethyl (EOM) and isobutoxymethyl. According to a particular embodiment the fluorescent dyes protected thiols heterocyclic group 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 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 polyhalo (CrC₄) Alkyl such as trifluoromethyl; iii) or heterocyclic: <img id="imgf000017_0001" he="29" wi="25" file="imgf000017_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 (Ci-C₄) Alkyl; preferably, R '^c to R '^d represent a group

p0115(Ci-C₄) Alkyl such as methyl; and An^" represents an against-ion. Y particularly represents a group selected from oxazolium, isoxazolium, thiazolium, isothiazolium, 1, 2,4-triazolium, 1, 2,3-triazolium, 1, 2,4-oxazolium, 1, 2,4-thiadiazolium, pyrylium, pyridinium , pyrimidinium, pyrazinium, pyridazinium, imidazolium and triazinium, benzoimidazolium benzoxazolium, benzothiazolium, these groups being optionally substituted by one or more (C₁-C₄) Alkyl especially methyl.

p0116In particular Y represents an alkali metal or a protecting group such as:

p0117> (CτC₄) Alkylcarbonyl such as methylcarbonyl or ethylcarbonyl;

p0118> Arylcarbonyl as phenylcarbonyl;

p0119> (-C₄) Alkoxycarbonyl; > Aryloxycarbonyl;

p0120> Aryl (-C₄) Alkoxycarbonyl;

p0121> (Di) (C₁-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl;

p0122> (-C₄) (Alkyl) arylaminocarbonyl;

p0123> Optionally substituted aryl such as phenyl; > Monocyclic 5- or 6-membered ring such as imidazolyl or pyridyl;

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 (C_rC₄) Alkyl such as methyl; > 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 (C_rC₄) Alkyl such as methyl;

p0125> Cationic heterocycle of formula below: <img id="imgf000018_0001" he="26" wi="24" file="imgf000018_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0126> Isothiouronium -C (Ha N) = N⁺H₂; Year^";

p0127> Isothiourea -C (NH₂) = NH;

p0128> SO₃^" M⁺ with M⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (I) and M⁺ are absent.

p0129In a particular embodiment of the invention, the dyes of the invention belong to either of the formulas (Ia) and (IIa) who have the ethylene group linking the pyridinium part to the phenyl ortho or para positions either 4-4 ', 4-2', 2- or 4 ':

p0130<img id="imgf000018_0002" he="59" wi="152" file="imgf000018_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> formulas (Ia) or (IIa) in which:

p0131^ (Het het N- and C¹ N, - identical or different, preferably identical, represent a saturated heterocyclic group or not, comprising monocyclic 5 to 7-membered ring and having 1 or 2 heteroatoms selected from nitrogen, oxygen and sulfur, particularly the heteroatom is a nitrogen atom; in particular the heterocycle is selected from pyrazolyl, piperazinyl, piperidinyl, morpholinyl and imidazolyl;

p0132> R, R ', R "i and R" i are identical or different, represent a hydrogen atom or a (C_rC₄) Alkyl; especially R, R ', R "i and R" represent a hydrogen atom;

p0133> R_g, R '_g, R "_g, R " 'g, R_h, R '_h, R "_h and R " '_h, Identical or different, represent a hydrogen atom or a (Ci-C₄) Particularly alkyl groups R_h and R '_hl R "_h and R " '_h are ortho to the pyridinium and represent a (C₁-C₄) Alkyl and R₉, R '_g, R "_g and R " '_g represent a hydrogen atom; > T_at and T_bRepresent a σ covalent bond, or a group chosen from:

p0134-N (R) -, -C (O) -N (R) -, -N (R) -C (O) -, -0-C (O) -, -C (O) -O- and - NOT⁺(R) (R⁰) -, With R and R ° are identical or different representing a hydrogen atom, a C₁-C₄ alkyl; particularly T₃ and T_b represent a σ bond> m, m ', n and n', identical or different, represent an integer ranging from O to 6 with m + n and m '+ n' preferably identical, the sum of m + n = m '+ n '= an integer ranging between 2 and 6; preferably m + n = m '+ n' is an integer equal to 2; > M 'is an anionic ion-against; and> Y is as defined above; it being understood that:

p0135- SY function of the dye of formula (IIa) may be in the covalent form

p0136-SY -SY Or ionic depending on the nature of Y and medium pH and

p0137- When the compound of formula (Ia) or (IIa) contains other cationic parts, it is associated with one or more anionic against ions to achieve electroneutrality of the formula (Ia) or (IIa).

p0138Advantageously, the dyes of formula (Ia) and (IIa) have the moiety

p0139f Het N- _etf Het "N in the para position of the phenyl ethylene ie connected to position the phenyl radical, ethylene being connected to the same position in phenyl 4 '. For example thiol fluorescent dyes, there may be mentioned the following compounds :

p0140¹<img id="imgf000019_0001" he="11" wi="114" file="imgf000019_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p01412M ' <img id="imgf000019_0002" he="11" wi="103" file="imgf000019_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000020_0001" he="35" wi="43" file="imgf000020_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0142<img id="imgf000020_0002" he="28" wi="110" file="imgf000020_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0143<img id="imgf000020_0003" he="15" wi="127" file="imgf000020_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0144<img id="imgf000020_0004" he="14" wi="129" file="imgf000020_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0145<img id="imgf000020_0005" he="17" wi="132" file="imgf000020_0005.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p014610

p0147<img id="imgf000020_0006" he="21" wi="133" file="imgf000020_0006.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0148December 11 <img id="imgf000021_0001" he="17" wi="112" file="imgf000021_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p014913

p0150<img id="imgf000021_0002" he="13" wi="113" file="imgf000021_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p015114

p0152<img id="imgf000021_0003" he="13" wi="109" file="imgf000021_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p015315

p0154<img id="imgf000021_0004" he="18" wi="144" file="imgf000021_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p015516 with M'représentant against an anionic ion.

p0156The protected thiol dyes of formula (II ') 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 (II "). 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^th ed., 2005, c. 5.

p0157We demonstrate this method by the method comprising i) generating thiol fluorescent dyes of formula (HH) by reduction of a fluorescent dye in two chromophores, heterocyclic, bearing a disulfide function -SS- (I ') and ii) protect by conventional methods, said thiol function of (HH) with the reagent 7 Y¹R to access the protected thiol fluorescent dyes of formula (H '). The thiol compound 6 can also be metallated with an alkali or alkaline earth metal

p0158Met * to give the thiolate fluorescent dye of formula (II ").

p0159<img id="imgf000022_0001" he="141" wi="141" file="imgf000022_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Y 'represents a protective group of thiol; Met^* representing an alkali metal or an alkaline earth metal, particularly sodium or potassium, provided that when the metal is a alkalino earth metal thiolate-2 chromophores function S^" may be associated with 1 Metal^{2 *}'With R₁, R₂R 3, R₄, R₉, R '_g, R_h, R'H, R, R '_> rn, n, Het and M 'are as defined above; Y 'represents a protective group of thiol; and R is a nucleofugic leaving group, for instance mesylate, tosylate, triflate or halide.

p0160Alternatively, one can react a protected thiol compound β>} with a protecting group Y 'as defined above, prepared according to one of procedures described in references cited previously, said protected thiol compound comprising at least one nucleophilic function with a sufficient amount, preferably equimolar to a "reactive fluorescent chromophore or a compound comprising such a" reactive fluorescent chromophore {Eq. In other J [terms a) comprises an electrophilic functional group to form a covalent bond Σ as can be schematized below in the preparation of fluorescent dyes of formula (II "):

p0161Y¹

p0162<img id="imgf000023_0001" he="67" wi="121" file="imgf000023_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R₉, R '_g, R_h, R'H. Ri. R ', m, n, Het, Y' and M 'are as defined above; ! Ku representing a nucleophilic group; (E representing an electrophilic group; and Σ the bond generated after attack of the nucleophile on the electrophile.

p0163For example, the Σ covalent bonds can be generated are listed in the table below from condensation of electrophiles with nucleophiles:

p0164<img id="imgf000023_0002" he="57" wi="147" file="imgf000023_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

p0165<img id="imgf000024_0001" he="187" wi="148" file="imgf000024_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

p0166* Activated esters of the general formula -CO-Part with Part representing a leaving group such as oxysuccinimidyl, oxybenzotriazolyle, optionally substituted aryloxy;

p0167** Acyl azides can rearrange to give isocyanates. An alternative to this method is to use a fluorescent chromophore having a electrophilic function acrylate (-OCO-C = C-) on which is carried out an addition reaction that will generate a Σ bond.

p0168We can also use a thiol reactive Y'-SH comprising a group Y¹ as defined above, the nucleophilic SH group can react on the carbon atom alpha to the halogen atom carried by the fluorescent chromophore (a Q to yield the protected thiol fluorescent dye of formula (H '):

p0169(H¹)

p0170<img id="imgf000025_0001" he="34" wi="96" file="imgf000025_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R, R 'g, Rh, R'H T_at, R ,, R '_yew m, n, Het, Y ', (II¹) And M 'are as defined above, and Hal representing a halogen atom nucleofugic such as bromine, iodine or chlorine.

p0171More 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:

p0172<img id="imgf000025_0002" he="39" wi="118" file="imgf000025_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> R '_c, R '_d, R₉, R '_g, R_h, R'H, R, R ', m, n, Het, Hal, An^" and M 'are as defined above.

p0173According to another variant it is possible to generate an imidazoline intermediate from the halide comprising the fluorescent chromophore xai) and a thioimidazoline (b ') to yield, after alkylation with an R-Gp reagent 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.

p0174<img id="imgf000026_0001" he="87" wi="132" file="imgf000026_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0175A variant is to use instead of the halide comprising the fluorescent chromophore (a ^) a chromophore comprising another type of nucleofuge such as tosylate or mesylate. According to another possibility, some fluorescent dyes protected thiol (H ") can be obtained by reacting a thiol compound with a compound having two carboxylic acid functions activated according to conventional methods (for example reaction with a carbodiimide or with thionyl chloride). The resulting product (CQ is then reacted with a fluorescent chromophore bearing a nucleophilic function (ç), eg primary or secondary amine type or of aliphatic alcohol type.

p0176<img id="imgf000026_0002" he="37" wi="121" file="imgf000026_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R₉, R 'g. Rh, R'H, R, R ', Het, T₃., Y ', m, n, M, E, Nu and (M' ') as defined above A further alternative is to use a thiolactone as described below: <img id="imgf000027_0001" he="106" wi="132" file="imgf000027_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0177A synthesis variant is to combine the first channel of the previous channel The. from two equivalents of the nucleophilic reagent here with a reactive disulphide dielectrophile (it it is possible to generate, after condensation the dichromophorique disulphide dye (I "), the latter being able to undergo reduction to form the heterocyclic fluorescent thiol dye which in turn can either be protected to form the protected thiol fluorescent dye (H ") or either be metallated with an alkali metal to yield the metallated heterocyclic thiol fluorescent dye (ir" κiétai):

p0178Met^*

p0179<img id="imgf000028_0001" he="164" wi="141" file="imgf000028_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0180According to another possibility, the protected thiol fluorescent dyes of formula (II ' ") can be obtained by reacting a compound comprising a thiol group protected by a group Y', and a hydroxy group activated in advance nucleofugic leaving group (CQ such as mesylate, tosylate, triflate or halide with a chromophore styrylpyridine (c'V E- (CR₁R₂JT (CR₃R₄J_not-SY (IP ")

p0181<img id="imgf000029_0001" he="35" wi="36" file="imgf000029_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0182with R₁, R₂, R₃, R₄, R₉, R '_B, Rh, R'H. R, R '. Het, T₈, Y ', m, n, (H ") and &lt;E are as defined above.

p0183By 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:

p0184<img id="imgf000029_0002" he="41" wi="121" file="imgf000029_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0185Another 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:

p0186<img id="imgf000029_0003" he="37" wi="121" file="imgf000029_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0187According to another possibility, the thiol fluorescent dyes of formula (I) according to the invention can be obtained by reacting a compound comprising a thiol group Y as defined above and an electrophilic group Q £ with a pyridinium compound comprising a group nucleophile. For example, it is possible to condense an aldehyde, ketone or thioaldehyde, thioketone when G 'represents an oxygen atom or a sulfur with an "activated methylene" as the alkylpyridinium (eQ to generate an ethylene bond> C = C <. This reaction is commonly referred to as condensation "Knoevenagel". By "activated methylenes" is meant those in which preferably comprises 2 or 4 position of the pyridinium group a methylene group RrCH₂-:

p0188<img id="imgf000030_0001" he="26" wi="111" file="imgf000030_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄Ra. Rb, R₉, R '_g, Rh, R'H, R, R ', T_at, Het, m, n, Y and M 'as previously defined and G is an oxygen or sulfur atom.

p0189Reference may be made to the book Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4^th 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.

p0190The 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 are metallated by also using the conventional methods known in the art such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4^th Ed₁ John Willey &amp; Sons, NY, 1992.

p0191The 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^th ed., 2005.

p0192Departures reagents are commercially available or accessible by conventional methods known in the art. For example it is possible to synthesize the reagent (I ') from 2 equivalents of pyridine derivative 1 and a disulfide reagent equivalent comprising two leaving groups Gp to yield the dipyridinium disulfide salt 3 which can condense turn composed with two equivalents aryl aldehyde group / f thioaldehyde to lead to T. Gp (CR₁ R₂)_mT_at- (CR₃R₄) - | Gp (CR₁R₂) J (CR₈R₄) JJs <img id="imgf000031_0001" he="14" wi="17" file="imgf000031_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000031_0002" he="17" wi="89" file="imgf000031_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0193<img id="imgf000031_0003" he="21" wi="26" file="imgf000031_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0194(I¹)

p0195Knoevenagel - 2H₂G with Gp representing a nucleofugic leaving group, for instance mesylate, tosylate, triflate or halide. The ion-against Gp^" the compounds (I ') above may be replaced by ions against M' of other types from methods known to those skilled in the art in particular by ion exchange resin.

p0196Unsymmetrical disulfide dyes of formula (I) can be synthesized in one step by reacting a thiol fluorescent dye unprotected with a protected thiol fluorescent dye with Y 'to form the disulphide dye of formula (1).

p0197)

p0198<img id="imgf000031_0004" he="67" wi="147" file="imgf000031_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₉, R '_g, R "_g, R "_gRt₁, R'H, R "h. R" hj Ri, R'H R "i> R" i, R, R'-i, RΣ_> R'2_> R31 R'3. R4, R '₄, M, m ', n, n', T_atT_b, Het, Het 'and M' are as defined above; Y 'represents a protective group of thiol.

p0199Reference may be made to the book Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4^th 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.

p0200The thiol fluorescent dyes formed can be converted to dyes protected thiol fluorescent -SY 'by the -SH thiol protection using standard protecting groups. The thiol fluorescent dyes are metallated by also using the conventional methods known in the art such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4^th Ed, John Willey &amp; Sons, NY, 1992.

p0201The 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^th ed., 2005. The 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 contain 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 of trimethoxyborohydride: sodium, lithium, potassium, calcium salts, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra-n butylammonium, benzyltriethylammonium); catechol borane.

p0202The dye composition according to the invention generally contains an amount of fluorescent dye 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.

p0203The 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.

p0204Among 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. The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

p0205Among 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

p0206Among these couplers, mention may be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

p0207The 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%.

p0208The 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. In 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 Ia sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

p0209The 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. The 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. Alternatively, the invention contains a reducing agent capable of reducing the disulphide bonds of keratin and / or the fluorescent dye of formula (I). This reducing agent is as defined above.

p0210The 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, thickening agents, inorganic or organic, and associative thickeners anionic, cationic, nonionic and amphoteric polymers, antioxidants, penetrants, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as for example, volatile or nonvolatile silicones, modified or not, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers, or conductive polymers.

p0211The 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.

p0212Of 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. The 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.

p0213Among 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.

p0214Among the alkalizing agents include, for example, ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (γ) below: ^xaa2

p0215<img id="imgf000035_0001" he="18" wi="29" file="imgf000035_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> ^ Wherein W₃ is a propylene residue optionally substituted with a hydroxyl group or an alkyl radical C₁-C₄ ; R_at-ι, R_at2, R a3 and R_a4, Identical or different, represent a hydrogen atom, an alkyl radical C₁-C₄ or hydroxy C₁-C₄.

p0216The 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.

p0217According 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 heterocyclic fluorescent dye of formula (I) or (II).

p0218This 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.

p0219This 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.

p0220According 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.

p0221According to another variant, the reducing agent is applied by post-treatment, after application of the composition containing at least one thiol fluorescent dye (I). The duration of post-treatment with the reducing agent may be short, for example 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.

p0222When the thiol fluorescent dye 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.

p0223For example it is possible to deprotect the SY function Y protecting group by adjusting the pH as follows:

p0224<img id="imgf000036_0001" he="91" wi="143" file="imgf000036_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0225The deprotection step can also be performed during a hair pretreatment step as for example, the reducing pretreatment of the hair.

p0226Alternatively, 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. A 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.

p0227Treatment 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, bromates alkali metals, persalts such as perborates and persulfates, and also enzymes, among which may be mentioned peroxidases, oxidoreductases with 2 electrons such as uricases and 4-electron oxygenases such as laccases.

p0228The use of hydrogen peroxide is particularly preferred. This 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).

p0229The 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. The 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 disulphide functions of keratin materials and / or the fluorescent dye of formula (I). One of these compartments may also contain one or more other dyes direct dye or oxidation dye.

p0230It 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 the fluorescent dye of formula (I); a third compartment contains an oxidizing agent.

p0231Alternatively, the dyeing device contains a first compartment containing a dye composition which comprises at least one protected thiol fluorescent dye of formula (II) and a second compartment containing an agent capable of deprotecting the protected thiol to free the thiol.

p0232Each 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. The examples which follow serve to illustrate the invention without limiting in nature. Fluorescent dyes of the examples below were fully characterized by spectroscopic and spectrometric methods conventional. EXAMPLES

SYNTHESIS EXAMPLES

p0234Example 1: Synthesis of dimethane sulfonate 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis {4-t (E) -2- (4-pyrrolidin-1-ylphényI) vinyl] pyridinium} [1]

p0235<img id="imgf000038_0001" he="35" wi="91" file="imgf000038_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0236Synthetic Scheme

,OH

HO

p0239O ti TEA

p0240'§ ~ CI AcOEt

p0241<img id="imgf000038_0002" he="102" wi="92" file="imgf000038_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Step 1: Synthesis of dimethanesulfonate disulfanediyldiéthane-2,1-diyl

p024210 g of 2,2'-dïthiodiéthanol and 14.44 g of triethylamine (TEA) are diluted in 100 ml of ethyl acetate (AcOEt). A 0⁰C, 16.35 g of methanesulfonyl chloride diluted in 35 ml of AcOEt are added dropwise to the reaction mixture with stirring rapide.7,22 g of TEA are introduced, stirring is continued at room temperature for 4:30. 8.2 g of methanesulfonyl chloride are added dropwise at 15⁰C, then stirring is maintained at room temperature for 17 hours. The precipitate is filtered and washed 3 times with 50 ml of AcOEt. The organic phases are extracted with 100 mL of ice water, 100 ml of water, 3 times 50 ml of a saturated solution of sodium hydrogen carbonate (NaHCO), with 2 times 20 ml of saturated sodium chloride ( NaCl), then were dried over sodium sulfate (Na₂SO₄) Anhydrous. The AcOEt is evaporated and 17.49 g of pale yellow translucent oil is collected and stored at -25⁰C. The analyzes indicate that the product complies and pure. Step 2: Synthesis dimethanesulfonate 1,1 '- (2,1 disulfanediyldiéthane-diyl) bis (4-methylpyridinium)

p02433.51 g of 4-picoline and 5 g of disulfanediyldiéthane-2,1-diyl dimethanesulfonate are diluted in 5 mL of N-methylpyrrolidinone (NMP) and heated to 80 ⁰C. under stirring for 2 hours. Stirring is maintained at room temperature for 17h. The reaction medium is supplemented with 50 ml of EtOAc, then filtered, washed 3 times with 100 mL of EtOAc (EtOAc), and dried under vacuum in presence of P₂O₅. 7.29 g of brown powder are recovered. The analyzes indicate that the product complies and pure. Step 3: Synthesis of dimethane sulfonate 1,1 '- (disulfanediyldiéthane-2,1-diyl) - bis {4 - [(E) -2- (4-pyrrolidin-1-yIphényl) vinyl] pyridinium} [1] 3 , 42 g of 4- (1-pyrrolidino) benzaldehyde, 10 ml of isopropanol (iPrOH), and 1, 69 mL of pyrrolidine were mixed with stirring for 10 minutes. 1, 18 ml of acetic acid are added and the mixture is stirred at room temperature for 20 minutes. Dimethanesulfonate 5 g of 1, 1 '- (disulfanediyldiéthane-2,1-diyl) bis (4-methylpyridinium) was suspended in 7 mL of iPrOH and 2 ml of methanol are added. The reaction mixture is stirred for 24 h at room temperature. The precipitate obtained is filtered, washed with 100 mL of acetone and then dried. 7.24 g of powder were recovered. The analyzes indicate that the product complies and pure. 1 H NMR (400 MHz, MeOH-d4) 2.03 - 2.06 (m, 8H), 2.71 (s, 6H), 3.3 - 3.4 (m, 12H), 4.7 (t, 4H), 6.6 (d , 4H), 6.99 (d, 2H), 7.57 (d, 4H), 7.8 (d, 2H), 7.93 (d, 4H), 8.53 (d, 4H). Example 2: Synthesis of de1,1 dimethanesulfonate "- (dîsulfanediyldiéthane-2,1-diyl) bis {4 - [(E) -2- (4-piperazin-1-yl-phenyl) vinyl] pyridinium} [2]

p0244<img id="imgf000040_0001" he="39" wi="96" file="imgf000040_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0245Synthetic Scheme

p0246<img id="imgf000040_0002" he="76" wi="97" file="imgf000040_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0247Synthesis of dimethanesulfonate de1,1 '- (disulfanediyldiéthane-2,1-diyl) bis {4 - [(E) - 2- (4-piperazin-1 -ylphényl) vinyl] pyridinium} [2]

p02482.5 g of 4-piperazin-1-yl-benzaldehyde, 10 mL of iPrOH, and 1, 06 mL of pyrrolidine were mixed with stirring for 10 minutes. 0.74 mL of acetic acid are added and the mixture is stirred at room temperature for 20 minutes. 3.22 g of dimethanesulfonate of 1, 1 '- (disulfanediyldiéthane-2,1-diyl) bis (4-methylpyridinium) was suspended in 7 mL of iPrOH and 2 ml of methanol are added. The reaction mixture is stirred for 24 h at room temperature. 100 uL of pyrrolidine and 70 .mu.l of acetic acid are added, stirring is continued for 48 hours at room temperature. The precipitate obtained is filtered, washed with 100 mL of acetone and then dried. 516 mg powder are collected. The analyzes indicate that the product complies and pure. NMR¹H (400 MHz, MeOH-c /₄) 3.17 (m, 8 H), 3.4 (t, 4H), 3.46 (m, 8 H), 4.81 (t, 4H), 7.04 (d, 4H), 7.21 (d, 2H), 7.67 (d, 4H), 7.88 (d, 2H), 8.08 (d, 4H) ,

p02498.69 (d, 4H)

p0250Example 3: Synthesis of dibromide of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis {2-

p0251[(E) -2- (4-pyrrolidin "1-yl-phenyl) vinyl] pyridinium} [3]

p0252<img id="imgf000041_0001" he="35" wi="42" file="imgf000041_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0253[3]

p0254Synthetic Scheme

p0255<img id="imgf000041_0002" he="53" wi="48" file="imgf000041_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0256iPrOH 24 20⁰C <img id="imgf000041_0003" he="20" wi="45" file="imgf000041_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0257<img id="imgf000041_0004" he="36" wi="45" file="imgf000041_0004.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0258[3] Step 1: Synthesis of dibromide of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis (2-methyl-pyridinium)

p0259A mixture of 56 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane, and 15 mL of A / -Méthylpyrrolidinone (NMP) is added dropwise to 35 g of 2-picoline under stirring at 80 ⁰C. The mixture (white suspension) is kept stirred for 30 minutes at 80 ⁰C, 100 ml of acetonitrile (ACN) are added, stirring is maintained at 80 ⁰C for 90 min. After cooling, the solid obtained is filtered, washed with 100 ml of ACN and dried. Collected 56.2 g of brown powder. 45 g of this powder are suspended in 300 mL of isopropanol (iPrOH) at reflux. Once the temperature lowered to 40⁰C, the solid is filtered, washed 3 times with 100 ml of iPrOH and dried under vacuum. beige product, 40.56 g. Analyzes in accordance with the expected structure. Step 2: Synthesis of dibromide of 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis {2- [(E) -2- (4-pyrrolidin-1-yl-phenyl) vinyl] pyridinium} [3] 2 g 4-pyrrolidin-1-yl-benzaldehyde solubilized in 4 mL of iPrOH and 0.93 mL of pyrrolidine were stirred at ambient temperature for 10 min. 0.65 mL of acetic acid are added to the reaction medium stirred at room temperature for 20 min. 2.65 g dibromide 1,1 '- (disulfanediyldiéthane-2,1-diyl) bis (2-methyl-pyridinium), predissolved in 5 mL of iPrOH and 2 mL of methanol are introduced into the medium. Stirring is maintained at 20⁰C for 17 h. 20 mL of iPrOH were added and stirring is continued at room temperature for 4 days. The precipitate is filtered, the red powder is dissolved with 50 ml of hot and stirring iPrOH. The precipitate obtained is filtered hot and then dried. 2.20 g of red powder are recovered. The analyzes indicate that the product complies and pure. NMR¹ H (400 MHz, DMSO-d₆) 1.93 (m, 8H), 3.15 (t, 4H), 3.22 (m, 8H), 4.89 (t, 4H), 6.48 (d, 4H), 7.05 (d, 2H), 7.51 - 7.56 (dd and d, 6H), 7.69 (d, 2H), 8.16 - 8.25 (d and dd, 4H), 8.5 (d, 2H).

p0260Example 4: Synthesis of dichloride of 1,1 '- {2,1-disulfanediylbistéthane diylimino (2-oxoethane-2,1 -diyI)]} bis {4 - [(E) -2- (4-pyrrolidin-1 -ylphényl) vinyl] - pyridinium} [4]

p0261O <img id="imgf000043_0001" he="26" wi="66" file="imgf000043_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0262Synthetic Scheme

p0263<img id="imgf000043_0002" he="127" wi="110" file="imgf000043_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0264Step 1: Synthesis of N, N '- (disulfanediyldiéthane-2,1-diyl) bis (2-chloroacetamide)

p026540.3 g of cystamine dihydrochloride are dissolved in 100 mL of water, 32 to 35% sodium hydroxide are added mL (pH 9.7) and the temperature is lowered to 5 ⁰C. 33.5 ml of chloroacetyl chloride are added dropwise, keeping the temperature less than 10 ⁰C and maintaining the pH between 7.9 and 9.3 by adding sodium hydroxide. The medium is kept stirred at room temperature for 2 hours. The precipitate is filtered, washed with 5 x 150 ml of water then dried under vacuum in presence of P₂O₅. 35.3 g of white powder are collected, the analysis indicates that the product complies. Step 2: Synthesis of dichloride of 1, r- {disulfanediylbis [ethane-2,1-diylimino (2-oxoethane-2,1-diyl)]} bis (4-methylpyridinium)

p02666.1 g N, N '- (disulfanediyldiéthane-2,1-diyl) bis (2-chloroacetamide) and 4.5 g of 4-picoline is dissolved in 50 ml of NMP and heated to 80 ⁰C for 19 h. After cooling the mixture, by successive precipitation in acetone and drying under vacuum, 9.2 g of salt were collected. Analyses show that the product complies. NMR¹H (400 MHz, D₂O): 2.61 (s, 6H), 2.82 (t, 4H), 3.56 (t, 4H), 5.31 (s, 4H), 7.85 (d, 4H), 8.51 (d, 4H) .

p0267Step 3: Synthesis of dichloride of 1,1 '- {disulfanediylbis [ethane-2,1-diylimino (2-oxoethane-2,1-diyl)]} bis {4 - [(E) -2- (4- pyrrolidin-1-yl-phenyl) -vinyl] - pyridinium} [4]

p0268700 mg of 4-pyrrolidin-1-ylbenzaldéhyde, 328 .mu.l of pyrrolidine, 232 .mu.l of acetic acid and 490 mg of dichloride of 1, 1 '- {disulfanediylbis [ethane-2,1-diylimino (2-oxoethane-2, 1-diyl)]} bis (4-methylpyridinium) are dissolved in 10 ml of isopropanol and kept stirred at room temperature for 3 h 30 min. The mixture was poured into 50 ml of dichloromethane solution / acetone 1: 1. A solid precipitates. It is filtered, washed with three times 20 ml of acetone and dried in vacuo. 620 mg of black powder is collected. Analyses show that the product conforms (LCMS: 100%; mass peak m / z = 367, corresponding to the tender).

p0269Example 5: Synthesis of 4 methanesulfonate - [(E) -2- (4-pyrrolidin-1-ylphenyl) vinyl] -1 - (2-sulfanylethyl) pyridinium [5]

p0270<img id="imgf000044_0001" he="12" wi="58" file="imgf000044_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0271[5]

p0272Synthesis of 4 salt - [(E) -2- (4-pyrrolidin-1-yl-phenyl) -vinyl] -1- (2-sulfanyl- ethyl) pyridinium [5] Synthetic Scheme

p0273<img id="imgf000045_0001" he="80" wi="103" file="imgf000045_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0274[5]

p027581 mg of the compound [2] are dissolved in 10 mL of water / ethanol mixture (1/1); 60 mg (2 eq.) Of hydrate of 3- hydrochloride [bis (2-carboxy-ethyl) phosphino] - propanoic acid dissolved in 1 ml of water and 21 mg (4 eq) of sodium bicarbonate dissolved in 1 mL of water are added to the mixture. After 30 minutes stirring at 4O⁰C under an inert atmosphere, the analyzes indicate that the mixture contains very predominantly the expected product [5].

p0276LC-MS analysis: LC-DAD (400-700 nm)

p0277Column: Waters XTerra MS C18 5 .mu.m (4.6 x 50) mm

p0278Mobile phase: A: water + 0.1% formic acid / B: Acetonitrile

p0279linear gradient: T (min)% A / B%: 0 min 95/5; 8 min 0/100

p0280Flow rate: 1 mL / min. Detection: UV LED Strip λ = 400-700nm

p0281Retention time t = 4.9 min.

p0282Relative purity> 95%

p0283MS (ESI +) m / z = 311 corresponds to the mass peak of monocation the expected product [5] EXAMPLE OF COLOUR

p0284Dyeing process - Compounds [1] to [3]

p0285Preparation of a composition A

p0286<img id="imgf000046_0001" he="41" wi="117" file="imgf000046_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0287Preparing a composition B

p0288<img id="imgf000046_0002" he="21" wi="103" file="imgf000046_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0289At 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 temperature room (the locks are turned over and reimpregnated after 15 minutes).

p0290After 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.

p0291Dyeing process - compound [5]

p029210 ml fresh solution of the compound [5] of Synthesis Example [5] are applied to a lock of 1 g hair of tone height 4 placed at the bottom of the same bowl for 30 minutes at room temperature (the locks returned and reimpregnated after 15 minutes). The locks were then rinsed with running water and dried. After staining, the wick of tone height 4 has become visually lighter than untreated control locks.

p0293Remanence vis-a-vis successive shampooing: The 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.

p0294Visual observations In shampoos, there is no visible bleeding, the shampoo foam and the rinsing water are not colored the lightening effect remains visible on the hair of tone height 4 thus treated.

p0295Results in the L * a^*b *: The color of the locks before and after the 5 washes was evaluated in the L * a * b * using a Spectrophotometer CM 2600 KONICA MINOLTA ®, (illuminant D65).

p0296In this system L * a^* b^*, L * is the intensity of the color, has^* indicates the axis of green / red color 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. Plus the value of a^* the higher the grade is red and the b * value is high more yellow the shade. The change in coloring between the HT hair strands 4 and the after treatment strands of hair (coloring, or staining and subsequent washings) is measured by (.DELTA.E) using the following equation:

p0297<img id="imgf000047_0001" he="9" wi="94" file="imgf000047_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0298In this equation, L *, a * and b * represent the values ​​measured before dyeing, and L₀*, at₀* and B₀* Represent the values ​​measured after treatment (dyeing or staining and subsequent washings).

p0299Plus the value of .DELTA.E, the greater the difference in color between HT4 locks and dyed locks is important. <img id="imgf000048_0001" he="114" wi="147" file="imgf000048_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0300The results in Table show that there is no significant difference of color variation exists even 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.

p0301Reflectance Results: lightening 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 with the reflectance of untreated lock of hair of tone height TH4.

p0302The reflectance is measured using a MINOLTA-spectrophotocolorimeter device KONIKA ®, CM 260Od and after irradiation of the hair with visible light in the wavelength range from 400 to 700 nanometers. Reflectance of the locks treated with the compounds 1, 2 and 3 to the application and after 5 shampoos

p03031 2 1-5 shampoos posed 2-5 sham products recommended <img id="imgf000049_0001" he="39" wi="116" file="imgf000049_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> oooooooooooooooc - m - Compound 3

p0304wavelength (nm) -^B - Compound 3-5 shampoos

p0305Figure 1

p0306Reflectance of the locks treated with compound 5 to the application and after 5 shampoos

p03075 5-5 shampoos

p0308<img id="imgf000049_0002" he="40" wi="116" file="imgf000049_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> ooooooooooooooo

p0309^ ON (OO CM tf CO CO CO ^ CM O OO O "tf - * ^ -tf LD LO -O -O lO tD CD CO CO CO N

p0310Wavelength (nm)

p0311Figure 2

p0312Firstly according recognizes Figures 1 and 2 that the reflectance of a lock of hair treated with a composition according to the invention is superior to that of untreated hair. The treated locks therefore appear brighter. In addition, results from the Figures 1 and 2 show that the reflectance of the locks of hair of tone height 4 treated with the composition of the invention change very little even 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.