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

Translation of description of equivalent WO 2007110532 A2

DYE COMPOSITION CONTAINING A FLUORESCENT DYE

THIOL / DISULPHIDE HETEROCYCLE AND EXTERNAL CATIONIC CHARGE,

METHOD FOR LIGHTENING KERATIN MATERIALS FROM

THIS DYE

p0005The invention relates to the coloring of keratin materials using fluorescent dyes thiols / disulfides comprising heterocycloalkyl.

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 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, 9_1, 259-264 ( 1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2,024,509.

p0013Furthermore it is known to protect or thiol functions in one molecule to be grafted to the hair before applying said hair WO 99/51 194. 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 FR 1 156407. 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 heterocycle group selected from dyes of formula (I), (II) or (III):

p0017<img id="imgf000004_0001" he="154" wi="124" 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), (II) or (III) wherein: > R_at and R '_at, Identical or different, represent an aryl group (-C C₄) Alkyl or a (CrC₆) Alkyl optionally substituted by hydroxyl or amino, (CrC₄) Alkylamino, (-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 R₃ and R '_at represent a (C₁-C₃) Alkyl optionally substituted by hydroxy group such as methyl or ethyl, or benzyl;

p0018> R_C represents a hydrogen atom, an aryl group (-C₄) Alkyl, a C₁-C₆ optionally substituted alkyl;

p0019> R_g, R '_g, R "_g, R "_g, R_h, 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, carboxyl, hydroxyl, trifluoromethyl, acylamino, alkoxy, C₁-C₄(Poly) hydroxyalkoxy, C₂-C₄, Alkoxycarbonyl alkylcarbonyloxy, alkylcarbonylamino, acylamino, carbamoyl, alkylsulfonylamino, amino-sulfonyl group, or a (C₁-C₄) Alkyl optionally substituted by a group selected from (C₁-C₄) 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 "_g, R "_g, R_h, R '_h, R "_h and R " '_h represent a hydrogen atom;

p0020> 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, (C₁-C₄) Dialkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, alkoxy, C₁-C₄(Poly) hydroxyalkoxy, C₂-C₄, Alkoxycarbonyl alkylcarbonyloxy, alkylcarbonylamino, acylamino, carbamoyl, alkylsulfonylamino, amino-sulfonyl group, or a (C₁-C₄) Alkyl optionally substituted by a group selected from (C₁-C₄) Alkoxy, hydroxy, cyano, carboxy, amino, (C₁-C₄) Alkylamino, (C₁-C₄) Dialkylamino, or else the two alkyl radicals borne by the nitrogen atom of the amino group form a heterocycle comprising 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;

p0021> R ,, R '; R "and R '" ,, identical or different, represent a hydrogen atom or a (C₁-C₄) Alkyl; particularly R ,, R '; R "and R '" ,, represent a hydrogen atom;

p0022> R-ι, R₂R 3, R₄, R '₁, R '₂, R '3 and R'₄, Identical or different, represent a hydrogen atom or a (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, hydroxy, cyano, carboxy, amino, (C₁-C₄) 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, R₂R 3, R₄, R'-i, R '₂, R '3 and R'₄Are hydrogen atoms or an amino group; particularly R₁, R₂, R₃ and R₄ represent a hydrogen atom; > T_at or T_b, Identical or different, represent: i) a σ covalent bond, ii) one or more radicals or combinations thereof selected from -SO₂-

p0023-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 a aryKd ^ Jalkyle; including T₃ and T_b represent a σ covalent bond or a group selected from -N (R) -, -C (O) -, -C (O) -

p0024N (R) -, -N (R) -C (O) -, -C (O) -N (R) -C (O) -, -0-C (O) -, -C (O) - O- and

p0025-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; iii) a heterocycloalkyl or heteroaryl radical, cationic or noncationic, preferably monocyclic, containing one or two heteroatoms, especially two nitrogen atoms, and in particular having from 5 to 7 members such as imidazolium, piperazinyl, piperazinium, homo-piperazinyl , homopipérazinium optionally substituted by a (C₁-C₄) Alkyl such as methyl;

p0026^/ V ^. _M^^NOT - - ^ TV. _MM ^ identical or different, represent a group

p0027I 'I cationic or non-heterocyclic, optionally substituted; in particular the heterocycle is monocyclic, saturated, and comprise a total of one to two nitrogen atoms and 5 to 8 members;

p0028> 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 T₃ and T_b represent a σ covalent bond, m + n = m '+ n' is an integer equal to 2; > M 'is an anionic ion-against; and

p0029> Y is i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N⁺R⁰¹R¹³R⁷R⁸ 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; provided that when the compound of formula (I), (II) or (III) contains other cationic parts, it is associated with one or more anionic against ions to achieve electroneutrality of the formula (I ), (II) or (III).

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

p0031The invention also relates to novel fluorescent dyes of formula (I), (II) or (III) 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.

p0032Furthermore, 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 allows to obtain a lightening of keratin materials such as keratin fibers, particularly dark keratin fibers and more particularly dark hair.

p0033Within the meaning of the invention, the term dark keratin material which exhibits a lightness L^* measured in the CIE L system^*at^*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 L^*100 = white.

p0034Within 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).

p0035The lightening of the hair is evaluated by the variation in "tone height" before and after application of the compound of formula (I), (II) or (III).

p0036The 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.

p0037The 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.

p0038An 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.

p0039Preferably, the composition should, after application to the hair, for example chestnut, bring the results below.

p0040- We are interested in hair reflectance performance when irradiated with visible light in the wavelength range from 400 to 700 nanometers.

p0041- It then compares the reflectance curves as a function of wavelength, of hair treated with the composition of the invention and the untreated hair.

p0042- The curve corresponding to the treated hair should show a reflectance in the range of wavelengths from 450 to 700 nanometers higher than the curve corresponding to the untreated hair.

p0043- This means that, in the wavelength range from 450 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 450 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.

p0044Preferably, 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 450 to 650 nanometers, and preferably in the wavelength range of 450-620 nanometers.

p0045Within the meaning of the present invention, and unless a different indication is given:

p0046- 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:

p0047• alkyl dC-iβ, preferably CRCS, optionally substituted by one or more radicals chosen from hydroxyl, alkoxy, C₁-C₂(Poly) hydroxyalkoxy C₂-C₄, Acylamino, amino substituted with two alkyl radicals, identical or different, in dC₄ , 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 from 5 to 7 members, preferably 5 or 6 membered saturated or unsaturated optionally substituted optionally comprising another heteroatom identical to or different from nitrogen; • a halogen atom such as chlorine, fluorine or bromine;

p0048• a hydroxyl group; alkoxy C₁-C₂ ;

p0049• a radical alkylthio, C₁-C₂ ; a radical (poly) hydroxyalkoxy C₂-C₄ ; • an amino radical;

p0050• a heterocycloalkyl with 5 or 6 members; a heteroaryl radical with 5 or 6 members optionally cationic, preferably imidazolium, optionally substituted with a (C₁-C₄) Alkyl, preferably methyl; • an amino radical substituted by one or two alkyl radicals, identical or different, -C₆ optionally bearing at least: i) hydroxy, 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 5 to 7 membered, saturated or unsaturated, optionally substituted and optionally comprises at least one other heteroatom from nitrogen or • an acylamino (-NR-COR ') 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 alkyl C₁-C₂ ; a carbamoyl radical ((R)₂N-CO-) in which the radicals R, identical or different, represent a hydrogen atom, an alkyl radical C₁-C₄ optionally bearing at least one hydroxyl group; an alkylsulfonylamino

p0051(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 C₁-C₄A phenyl radical; 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,

p0052• a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);

p0053• a cyano group; • 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; 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, alkoxy, C₁-C₄(Poly) hydroxyalkoxy, C₂-C₄, An alkylthio dC₂ ; • alkylcarbonylamino (RCO-NR'-) in which the radical R 'is a hydrogen atom, an alkyl radical dC₄ 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 dC₄ 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; • alkylcarbonyloxy (RCO-O-) in which the radical R is an alkyl radical

p0054-C₄And amino substituted with two alkyl groups are identical or different -C₄ 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; alkoxycarbonyl (RO-CO-) in which the radical R is an alkyl radical -C₄And amino substituted with two alkyl groups are identical or different -C₄ 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;

p0055- 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;

p0056- 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;

p0057- 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;

p0058- 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 atom, 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;

p0059- 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;

p0060- 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 ;

p0061- 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 ;

p0062- An "alkyl group" is a hydrocarbon radical C₁-C₁₆Linear or branched, preferably C₁-C₈ ;

p0063- 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, C₁-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 carrying them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom

p0064+ Different or not from nitrogen; v) or a quaternary ammonium group -N R'R "R" ',

p0065M wherein R ', R ", R"', identical or different, represent an atom

p0066+ Hydrogen, or an alkyl group -C₄Or else -N R'R "R" 'forms a heteroaryl such as imidazolium optionally substituted by a group dC₄ alkyl, and M represents the against-ion of the organic acid, mineral acid or of the corresponding halide;

p0067- A "alkylene chain" is a divalent chain C₁-C₁8; especially -C₆, Especially -C₂ when the chain is linear; optionally substituted by one or more, identical or different, halogen atoms or groups selected from hydroxy, alkoxy, (di) (C₁-C₄) (Alkyl) amino, R^at-Z^at-C (Z^b) - With Z^at, Z^b, Identical or different, representing an oxygen, sulfur, or NR^at'And R^atRepresenting an alkali metal, a hydrogen atom, or an alkyl group and R^at'Representing a hydrogen atom or an alkyl group;

p0068- A "alkoxy radical" is an alkyl-oxy radical or alkyl-O- in which alkyl is a hydrocarbon radical, linear or branched C₁-C₁6 preferentially ECRC; - A "alkylthio" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched CRCI₆ preferably -C₈ ; when the alkylthio group is optionally substituted, this means that the alkyl group is optionally substituted as defined above;

p0069- The limits delimiting the extent of a range of values ​​are included in this range;

p0070- 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 acid ethoxysulfinic; 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 ;

p0071- 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 oroborate tétraflu. Fluorescent dyes having heterocyclic group of formula (I), (II) or (III) are compounds capable of absorbing in the UV or visible radiation at a wavelength λ_atbs between 250 and 800 nm and capable of réémettrent in the visible range at a transmission wavelength λ_em between 400 and 800 nm.

p0072Preferably fluorescent compounds heterocyclic group of the invention are dyes capable of absorbing in the visible λ_atbs 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), (II) or (III) 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. A particular embodiment of the invention relates to fluorescent dyes heterocyclic group of formula (I), (II) or (III) wherein m is 0.

p0073According to a particular embodiment of the invention, the fluorescent dyes of the invention the heterocycle of formula: <img id="imgf000014_0001" he="14" wi="42" file="imgf000014_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0074represents a group or not, <img id="imgf000014_0002" he="16" wi="80" file="imgf000014_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> optionally substituted; in particular the heterocycle is monocyclic, saturated, and comprises a total of two nitrogen atoms and is composed of 5 to 8 members. Particularly the heterocyclic is selected from piperazinyl, homopiperazinyl, hexahydro-1, 4-diazepinyl, and piperazinium, homopipérazinium or hexahydro-1, 4- diazepinium optionally substituted with a (dC₄) Alkyl. According to another embodiment, the thiol fluorescent dyes heterocyclic group of formula (I), (II) or (III) in which the heterocycle:

p0075heterocyclic; monocyclic,<img id="imgf000015_0001" he="17" wi="92" file="imgf000015_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> saturated ring comprising in total a single nitrogen atom composed of 5 to 7 members.

p0076Particularly the heterocyclic is selected from pyrrolidinyl, piperidinyl and azepanyl.

p0077The fluorescent compounds of the invention of formula (III) 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.

p0078A specific embodiment relates to fluorescent dyes thiols heterocyclic group of formula (III) function SY where Y is a hydrogen atom, or an alkali metal. Preferably Y is hydrogen.

p0079According to another embodiment of the invention, in formula (III) above, Y is a protecting group known in the art such as those described in the books "Protective Groups in Organic Synthesis", TW Greene, John Willey &amp; Sons ed, NY, 1981, pp.193-217.

p0080"Protecting Groups" P. Kocienski, Thieme, 3^th ed., 2005, c. 5.

p0081Especially when Y represents a group protecting the thiol function, Y is selected from the following radicals:

p0082• (-C₄) Alkylcarbonyl; • (-C₄) Alkylthiocarbonyl;

p0083• (C-rC₄) Alkoxycarbonyl;

p0084• (-C₄) Alkoxythiocarbonyl;

p0085• (C "rC₄) Alkylthio-thiocarbonyl;

p0086• (di) (C₁-C₄) (Alkyl) aminocarbonyl; • (di) (-C₄) (Alkyl) aminothiocarbonyl;

p0087• arylcarbonyl as phenylcarbonyl;

p0088• aryloxycarbonyl;

p0089• aryl (Ci-C₄) Alkcoxycarbonyle;

p0090• (di) (-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl; • (Ci-C₄) (Alkyl) arylaminocarbonyl;

p0091• carboxyl;

p0092• SO₃ ; M⁺ with M⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (III) and M⁺ are absent; • optionally substituted aryl such as phenyl, dibenzosuberyl, or

p00931, 3,5-cycloheptatrienyl,

p0094• 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, 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 1 of 1-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 (-C₄) Alkyl such as methyl, or polyhalo (-C₄) Alkyl such as trifluoromethyl; iii) or tricyclic ABC:

p0095<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, 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; • 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 / tetrahydro-pyrimidinyl which is optionally substituted by one or more groups such as (C₁-C₄) Alkyl, oxo or thioxo; or heterocycle represents the following group:

p0096<img id="imgf000017_0001" he="30" wi="38" file="imgf000017_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 (C₁-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 represents a against ion;

p0097- 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;

p0098- Isothiourea -C (NR '^cR '^d) = NR '^e R '^c, R '^d and R '^e as defined above;

p0099• (di) aryl (-C₄) Alkyl optionally substituted such as 9-anthracenylmethyl, diphenylmethyl or phenylmethyl optionally substituted by one or more groups chosen in particular from (C₁-C₄) Alkyl, (C₁-C₄) BlCOXy such as methoxy, hydroxy, (C₁-C₄) Alkylcarbonyl, and (di) (C₁-C₄) (Alkyl) amino such as dimethylamino;

p0100• (di) heteroaryl (-C₄) Akyle optionally substituted, the heteroaryl group is in particular cationic or non monocyclic having 5 or 6 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) heteroaryl-methyl or (di) heteroarylethyl;

p0101• CR¹R²R³ with R¹, R² and R³ identical or different, representing a halogen atom or a group selected from:

p0102- (C₁-C₄) Alkyl; - (C₁-C₄) Alkoxy;

p0103- Optionally substituted aryl such as phenyl optionally substituted with one or more groups such as (CrC₄) Alkyl, (C₁- C₄) Alkoxy, or hydroxyl;

p0104- Optionally substituted heteroaryl, such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted by a group

p0105(Ci-C₄) Alkyl;

p0106- P (Z¹) R '¹R '²R '³ R '¹And R '² identical or different, representing a hydroxyl, (CrC₄) Alkoxy or alkyl, R '³ represents a hydroxy group or (CrC₄) Alkoxy, and Z¹ represents an atom of oxygen or sulfur;

p0107• hindered cyclic such as adamantyl; and

p0108• alkoxy (-C₄) Alkyl optionally substituted such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

p0109According to a particular embodiment the fluorescent dyes protected thiols heterocyclic group of formula (III) 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-membered to 1 of 1 such as cationic 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) As alkyl trifluoromethyl; iii) or heterocyclic:

p0110<img id="imgf000019_0001" he="30" wi="28" 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.

p0111Y 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 groups (-C₄) Alkyl especially methyl.

p0112Particularly the fluorescent dyes of formula (III) include a group Y is an alkali metal or a protecting group such as:

p0113> (Ci-C₄) Alkylcarbonyl such as methylcarbonyl or ethylcarbonyl; > Arylcarbonyl as phenylcarbonyl;

p0114> (Ci-C₄) Alkoxycarbonyl;

p0115> Aryloxycarbonyl;

p0116> ^ D ^ ary Jalcoxycarbonyle;

p0117> (Di) (C₁-C₄) (Alkyl) aminocarbonyl as dimethylaminocarbonyl; > (C₁-C₄) (Alkyl) arylaminocarbonyl;

p0118> Optionally substituted aryl such as phenyl;

p0119> Monocyclic 5- or 6-membered ring such as imidazolyl or pyridyl;

p0120> 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 (-C₄) Alkyl such as methyl;

p0121> Cationic bicyclic heteroaryl 8 to 1 of 1 links including benzoimidazolium or benzoxazolium; these groups being optionally substituted by one or more identical or different groups (-C₄) Alkyl such as methyl;

p0122> Cationic heterocycle of formula below:

p0123<img id="imgf000020_0001" he="28" wi="25" file="imgf000020_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0124> Isothiouronium -C (NH₂) = N⁺H₂; Year^"; > Isothiourea -C (NH₂) = NH;

p0125> SO₃^"M⁺ with M⁺ representing an alkali metal such as sodium or potassium, or else M 'of formula (III) and M⁺ are absent.

p0126In a particular embodiment of the invention, the dyes of the invention belong to the formula (I), (II) or (III) include ethylene group linking the pyridinium part to the phenyl ortho or para positions in either 4 -4 ', 2-2', 4-2 'or 2-4'.

p0127Another embodiment of the invention relates disulfide dyes of formula (I) symmetrical ie R_at, R₉, R '_g, Rh, R'H, R, R ', R2, R3, R₄T₃, M, n are equal to R '_at, R "_g, R "_g, R "_h, R "_hR ",, R" ,, R '1, R' 2, R's, R '₄T_b, M 'and n', respectively. Examples of fluorescent dyes of the invention, we may notably mention the following compounds:

p0128<img id="imgf000020_0002" he="69" wi="140" file="imgf000020_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Year^"<img id="imgf000021_0001" he="179" wi="154" file="imgf000021_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0129<img id="imgf000022_0001" he="211" wi="154" file="imgf000022_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000023_0001" he="188" wi="154" file="imgf000023_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0130<img id="imgf000024_0001" he="219" wi="154" file="imgf000024_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000025_0001" he="227" wi="154" file="imgf000025_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0131<img id="imgf000026_0001" he="198" wi="153" file="imgf000026_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000027_0001" he="34" wi="60" file="imgf000027_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p013248

p0133<img id="imgf000027_0002" he="13" wi="134" file="imgf000027_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p013449

p0135M ', and An-, identical or different, representing an anionic against ion; and M⁺ representing an alkali metal.

p0136The protected thiol dyes of formula (IM ") can be synthesized in two stages. The first stage of preparing the non-thiol dye (IH ') according to methods known to the skilled artisan 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 (IM "). 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.

p0137We demonstrate this method by the method comprising i) generating fluorescent dyes heterocyclic thiols of formula (IH ') by reduction of a fluorescent dye in two chromophores, heterocyclic, bearing a disulfide function -SS- such as (I¹) And ii) to be protected according to conventional methods said thiol (IM ') to access the protected thiol fluorescent dyes of formula (M "): <img id="imgf000028_0001" he="87" wi="144" file="imgf000028_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R, R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'H, R ,, R ',, m, 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.

p0138Alternatively, 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 a sufficient amount, preferably equimolar to a "reactive fluorescent chromophore" or a compound comprising such a "reactive fluorescent chromophore (a). In other words (a) comprises an electrophilic functional group to form a covalent bond as Σ can be summarized below:

p0139<img id="imgf000028_0002" he="39" wi="124" file="imgf000028_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000029_0001" he="39" wi="96" file="imgf000029_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R, R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'H R, R ',, m, n, Het, Y' and M 'are as defined above; 5VW representing a nucleophilic group; £ representing an electrophilic group; and Σ the bond generated after attack of the nucleophile on the electrophile.

p0140For example, the Σ covalent bonds can be generated are listed in the table below from condensation of electrophiles with nucleophiles:

p0141<img id="imgf000029_0002" he="135" wi="157" file="imgf000029_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" /> carboxylic acids Amino iarboxamides

p0142Esters carboxylic acids Alcohols

p0143Carbodiimides carboxylic acids M-acylureas or anhydrides

p0144Diazoalkanes carboxylic acids Esters

p0145Epoxides Thiols fhioéthers

p0146Haloacetamides Thiols fhioéthers

p0147Esters Amino imidic Amidines

p0148Isocyanates Amino Ureas

p0149Urethanes Isocyanates alcohols

p0150Isothiocyanates Amino fhiourées

p0151Maleimides thiols fhioéthers

p0152Sulfonic esters Amino Alkylamines

p0153Sulfonic esters Thiols fhioéthers

p0154sulfonate esters carboxylic acids esters

p0155sulfonate esters Alcohols Ethers

p0156Amino Sulfonamides sulfonyl halides activated esters of the general formula -CO-Share with a group representing Part starting as oxysuccinimidyl, oxybenzotriazolyle, optionally substituted aryloxy;

p0157^** acyl azides can rearrange to give isocyanates.

p0158An alternative to this method is to use a fluorescent chromophore having an electrophilic acrylate function (-OCO-C = C-) on which is carried out an addition reaction that will generate a Σ bond.

p0159Use may also be a thiol reagent Y'-SH comprising a Y 'group as defined above, the nucleophilic SH group can react on the carbon atom alpha to the halogen carried by the fluorescent chromophore atom (a¹) To yield the protected thiol fluorescent dye of formula (IM "): <img id="imgf000031_0001" he="41" wi="120" file="imgf000031_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'n T₃, R₁, R ', m, n, Het, Y', (Ml ") and M 'are as defined above, and Hal representing a halogen atom nucleofugic such as bromine, iodine or chlorine.

p0160More 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 thioimidazolium (β), the reaction scheme is as follows:

p0161<img id="imgf000031_0002" he="56" wi="146" file="imgf000031_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R_at, R '_c, R'd, R, R 'g, Rh, R'H, R, R', m, n, Het, Hal, An^" and M 'are as defined above.

p0162A variant is to use instead of the halide comprising the fluorescent chromophore (a¹) A chromophore comprising another type of nucleofuge such as tosylate or mesylate. According to another possibility, some fluorescent protected heterocyclic thiol dyes (IM ") can be obtained by reacting a protected 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 (s) is then reacted with a fluorescent chromophore bearing heterocyclic nucleophilic function (ç), eg primary or secondary amine type or of aliphatic alcohol type or aromatic such as phenol. J_not-SY¹ (III¹¹¹)

p0163<img id="imgf000032_0001" he="39" wi="99" file="imgf000032_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁, R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'n, R., R., Het, T₃, Y ', m, n, M', ^&lt;£, 5VM and (M ") as defined above.

p0164According to another possibility, fluorescent dyes heterocyclic protected thiol of formula (III) 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 (cT) such as mesylate, tosylate, triflate or halide with a fluorescent chromophore £ {} carries a nucleophilic amino function on the heterocyclic moiety of Het.

p0165<img id="imgf000032_0002" he="66" wi="109" file="imgf000032_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0166With R, R₂, R₃, R₄, R₃, R₉, R 'g, Rh, R'H, R ,, R' ,, Het, T₃, Y ', n, M', Σ and E are as defined above.

p0167By 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: <img id="imgf000033_0001" he="43" wi="140" file="imgf000033_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0168Another 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:

p0169<img id="imgf000033_0002" he="43" wi="141" file="imgf000033_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0170According to another possibility, the protected thiol fluorescent dyes of formula (III) 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 compound comprising a group nucleophile. for example, one can condense an aldehyde or ketone when G represents an oxygen atom with an "activated methylene" such as alkylpyridinium (e) for generating an ethylene bond> C = C <. This reaction . is commonly known condensation "Knoevenagel" by "activated methylene" it implies for example those mentioned in the patent DE19951 134 include particularly the 1, 2-dialkylpyridinium including the 1, 2-dimethylpyridinium:

p0171<img id="imgf000033_0003" he="36" wi="123" file="imgf000033_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₁ , R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'n, R ,, R ',, Het, T₃, M, n, Y and M 'such that defined above and G is oxygen, sulfur or a group N (R) with R representing a hydrogen atom or a (C₁- C₄) Alkyl.

p0172An alternative to this method is to achieve i) a condensation "Knoevenagel" an aldehyde or ketone having an amino group to nucleophilic heterocycle Het {g} with an "activated methylene" such as alkylpyridinium (e) to lead to the styryl-heterocyclic intermediate (h). The latter may then ii) react with a cyclic monomer containing at least one function thiolactam to yield, after ring opening of the heterocyclic thiol fluorescent dye (MIa):

p0173<img id="imgf000034_0001" he="74" wi="115" file="imgf000034_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0174with R₁, R₂, R₃, R₄, R₃ R₉, R '_g, R_h, R'H, R ,, R ',, Het, n and M' as previously defined, G and G ', same or different oxygen, sulfur or a group N (R) with R representing a hydrogen atom or a (C₁- C₄) Alkyl.

p0175Alternatively, when the reactant (g¹) Comprises a Het group to amino group exocyclic, the fluorescent dye to the amide group, thioamide, or amidine guanidine is obtained

p0176<img id="imgf000035_0001" he="76" wi="121" file="imgf000035_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" />

p0177With R, R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'H, R ,, R ',, Het, n, M, G and G', as defined above and R 'represents a hydrogen atom, or an alkyl group. It being understood that the heterocycle of the amine reagent (£ ç) may be protected and deprotected.

p0178Reference may be made to the book Advanced Organic Chemistry, 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. The thiol fluorescent dyes formed can be converted into protected thiol fluorescent dyes -SY 'by the -SH thiol protection using standard protecting groups.

p0179The protected thiol dyes can be deprotected by conventional routes.

p0180The disulphide dyes of formula (I) can be synthesized in two steps. The first step of preparing the non-thiol dye (III) by the methods described above. And the second step of oxidizing the unprotected thiol dye (III) to form the disulphide dye of formula (I¹) Symmetrical. The oxidation of a disulfide thiol is done according to conventional methods known to those skilled in the art, for example using hydrogen peroxide. <img id="imgf000036_0001" he="48" wi="84" file="imgf000036_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0181Alternatively, may be reacted one equivalent of a disulfide compound (b ") according to procedures described in the books mentioned above, said disulfide compound comprising two nucleophilic functional groups with a sufficient amount of a" fluorescent chromophore reagent "or a compound comprising such a" reactive fluorescent chromophore "(a) as at least two equivalents. this means (a) comprises an electrophilic functional group to form a covalent bond Σ, to yield a disulfide dye formula (I ") as may be shown schematically below:

p0182<img id="imgf000036_0002" he="88" wi="146" file="imgf000036_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R, R₂R 3, R₄, R_at, R, R '_g, Rh, R'H, R, R ', m, n, Het and M' are as defined above; Nu representing a nucleophilic group;¹E representing an electrophilic group; and Σ the bond generated after attack of the nucleophile on the electrophile. For example, the Σ covalent bonds can be generated are listed in the table above from condensation electrophiles with nucleophiles.

p0183According to another possibility, some disulfide fluorescent dyes (I ") can be obtained by reacting at least two equivalents of a" reactive fluorescent chromophore (C) comprising a nucleophilic moiety with one equivalent of a disulfide compound dielectrophile (d " ) to yield the disulphide dye (I "):

p0184<img id="imgf000037_0001" he="39" wi="144" file="imgf000037_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0185with R₁, R₂, R₃, R₄, R₃, R₉, R '_g, R_not, R 'n R, R ,, Het, m, n, M, ^&lt;£, 9ûι and (I ") as defined above.

p0186According to another possibility, the heterocyclic disulfide fluorescent dyes of formula (I¹") Can be obtained by reacting a compound (d ') comprising a disulfide group, and a hydroxy group activated in advance nucleofugic leaving group Cp, as for example mesylate, tosylate, triflate or halide with a fluorescent chromophore {£ ) carrying a nucleophilic amino function on the heterocyclic part of Het.

p0187<img id="imgf000038_0001" he="79" wi="145" file="imgf000038_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0188with R₁, R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'H, R ,, R ',, Het, n, M', and Pc are as defined above.

p0189For example a compound containing a disulfide 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 to yield styryl disulfide dye individual (the " 'a):

p0190<img id="imgf000038_0002" he="83" wi="119" file="imgf000038_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0191Another alternative arises from the use of halides as nucleofugic leaving group to a disulfide compound may be substituted by a secondary amino function for example carried by a fluorescent chromophore styryl: <img id="imgf000039_0001" he="41" wi="119" file="imgf000039_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> IEL

p0192According to another possibility, the disulfide fluorescent dyes (I) according to the invention can be obtained by reacting a compound having a disulfide group as defined above and an electrophilic group (f ") 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 (e) for generating an ethylene bond> C = C <. This reaction is commonly . called condensation "Knoevenagel" by "activated methylene" it implies for example those mentioned in the patent DE19951 134 include particularly the 1, 2 dialkylpyridinium including the 1, 2-dimethylpyridinium:

p0193<img id="imgf000039_0002" he="88" wi="135" file="imgf000039_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0194(I¹) With R, R₂, R₃, R₄, R₃, R₉, R '_g, Rh, R'H, R ,, R ',, Het, T₃, M, n, (I) and M 'such that defined above and G is oxygen, sulfur or a group N (R) with R representing a hydrogen atom or a (d- C₄) Alkyl.

p0195Reference may be made to the book Advanced Organic Chemistry, 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.

p0196The 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 with Y 'to form the disulphide dye of formula (I).

p0197<img id="imgf000040_0001" he="106" wi="140" file="imgf000040_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₃, R '_at, R₉, R '_g, R "_g, R "_g, Rh, R'H, R "h, R" h, R, R ', R "ι, R"' ι, m, m ', n, n', T₃T_b, Het Het ', (I) and M' are as defined above; Y 'represents a protective group of thiol.

p0198Unsymmetrical disulfide dyes of formula (II) can be synthesized in one step by reacting a protected thiol fluorescent dye with a non-protected thiol compound to form the disulphide dye of formula β). <img id="imgf000041_0001" he="74" wi="138" file="imgf000041_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> with R₃, R '_at, R₉, R '_g, R "_g, R "_g, Rh, R'H, R "h, R" h, R, R ', R "ι, R"' ι, R'c, m, m ', n, n', T₃T_b, Het, Hef, (II) and M 'are as defined above; Y 'represents a protective group of thiol. The composition of the invention contains at least one heterocyclic fluorescent dye of formula (I), (II) or (III). Furthermore the presence of at least one fluorescent dye of formula (I), (II) or (III), 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.

p0199The dye composition according to the invention generally contains an amount of heterocyclic fluorescent dye of formula (I), (II) or (III) 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.

p0200The dye composition may also contain additional direct dyes. These direct dyes are chosen, for example direct dyes nitrated neutral, acidic or cationic, neutral azo direct dyes, acidic or cationic tetraazapentamethine dyes, quinone dyes and in particular anthraquinone, acidic or cationic direct dyes, azine direct dyes, triarylmethane direct dyes, indoamine and natural direct dyes.

p0201Among 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.

p0202The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratin fibers.

p0203Among 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

p0204Among these couplers, mention may be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts. The 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%.

p0205The 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.

p0206In 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.

p0207The 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.

p0208The 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.

p0209Alternatively, the invention contains a reducing agent capable of reducing the disulphide bonds of keratin. 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 genera LEMENT between 3 and 14 approximately, and preferably between approximately 1 to 1 5. 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, inorganic acids or organic, 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 mono-, di- and triethanolamine and derivatives thereof, sodium or potassium hydroxides and compounds formula (γ) below:

p0215^R^ 1 _/^Ra2

p0216N - W₃-NOT

p0217^Ra4 ^Ra3 ^ wherein W_at is a propylene residue optionally substituted with a hydroxyl group or an alkyl radical C₁-C₄ ; R_ati, R_a2. R a3 and R_a4, Identical or different, represent a hydrogen atom, an alkyl radical C₁-C₄ or hydroxy C₁-C₄.

p0218The 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.

p0219According 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), (II) or (III) .

p0220This 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.

p0221This 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.

p0222When the heterocyclic thiol fluorescent dye (III) comprises a group Y protecting the thiol group, 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="imgf000045_0001" he="98" wi="152" file="imgf000045_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" /> The deprotection step can also be performed in the heart of a hair pretreatment step as for example, the reducing pretreatment of the hair.

p0225Alternatively, the reducing agent is added to the dye composition containing at least one heterocyclic fluorescent dye (I), (II) or (III) at the time of use.

p0226According to another method, the composition comprising at least one heterocyclic fluorescent dye of formula (I), (II) or (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair. According 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), (II) or (III). 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. According to one embodiment particularly the reducing agent is a thiol agent or borohydride as described above.

p0227In the dyeing process another alternative is to apply the fluorescent dye of formula (I) or (II) together with the gearbox. A particular embodiment of the invention relates to a method wherein the fluorescent dye of formula (I), (II) or (III) can be applied directly to the hair without reducing agents, free of reducing pretreatment or reducing aftertreatment.

p0228Treatment 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 persulphates, and enzymes, among which mention may be made peroxidases, oxido 2-electron such as uricase and 4-electron oxygenases such as laccases.

p0229The 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), (II) or (III). The 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 180 ° C. The invention also relates to a multi-compartment device or "kit" in which a first compartment contains a dye composition comprising at least one heterocyclic fluorescent dye of formula (I), (II) or (III) and a second compartment contains a reducing agent capable of reducing the disulphide functions of keratin materials. 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 heterocyclic thiol fluorescent dye of formula (I), (II) or (III); a second compartment contains a reducing agent capable of reducing the disulfide bond of keratin materials and / or the disulfide bond of the dyes of formula (I) or (II); a third compartment contains an oxidizing agent.

p0231Alternatively, the dyeing device contains a first compartment containing a dye composition which comprises at least one fluorescent dye protected thiol of formula (III) 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.

p0233The following examples serve to illustrate the invention without being limiting in nature. Fluorescent dyes of the examples below were fully characterized by spectroscopic and spectrometric methods conventional.

EXAMPLES

SYNTHESIS EXAMPLES

p0236Example 1: Synthesis of dimethyl 4,4 '- {disulfanediylbis [ethane-2,1-diyl piperazine-4,1-diyl-4,1-phenylene (E) ethene-2,1-diyl]} bis ( 1-methylpyridinium)

p0237[1]

p0238<img id="imgf000048_0001" he="30" wi="108" file="imgf000048_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0239[1]

p0240Synthetic Scheme

p0241<img id="imgf000048_0002" he="47" wi="53" file="imgf000048_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

- N N

O

p0244<img id="imgf000048_0003" he="50" wi="108" file="imgf000048_0003.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0245[1] Step 1: Synthesis of 4,4 '- [disulfanediylbis (ethane-2,1-diylpipérazine-4,1-diyl)] - dibenzaldehyde

p02462.5 g of 4-piperazin-1-yl-benzaldehyde, 1, 37 g of 1-bromo-2 - [(2-bromoethyl) - disulfanyl] ethane, 7.3 g of potassium carbonate (K₂CO₃), And 20 mL of N-methylpyrrolidinone (NMP) were mixed at 75 ° C for 55 h. The product is purified by chromatography on silica gel (eluent: acetone / heptane 80/20 then dichlormethane / methanol 90/10). 469 mg of yellow oil are recovered. The analyzes indicate that the product complies. Step 2: Synthesis of dimethyl 4,4 '- {disulfanediylbis [ethane-2,1-diyl- piperazine-4,1-diyl-4,1-phenylene (E) ethene 2,1-diyl]} bis ( -méthylpyridinium 1) [1] 469 mg of 4,4 '- [disulfanediylbis (ethane-2,1-diylpipérazine-4,1-diyl)] dibenzaldehyde, 5 mL of isopropanol (iPrOH), 415 mg of methyl 1 , 4-dimethylpyridinium, 80 mg of pyrrolidine, 56 mg of acetic acid and 5 ml of dichloromethane are mixed at room temperature for 24 h then at 40 ° C for 24 h. After cooling the mixture, 20 ml of acetone are added, the precipitate obtained is filtered, washed with 10 mL of isopropanol, then with 3 times 25 ml of acetone, and dried. 610 mg of red powder are recovered. The analyzes indicate that the product complies.

p0247NMR ¹ H (400 MHz, MeOH ^₄) 2.68 (m, 8H), 2.78 (t, 4H), 2.95 (t, 4H), 3.37 (m, 8H), 3.68 (s, 6H), 4.24 (s, 6H), 7 (d, 4H), 7.16 (d, 2H), 7.62 (d, 4H), 7.82 (d, 2H), 8.01 (d, 4H), 8.56 (d, 4H)

p0248Example 2: Synthesis of methyl 1-methyl-4 - ((E) -2- {4- [4- (2-sulfanyl- ethyl) piperazin-1-yl] phenyl} vinyl) pyridinium [2]

p0249<img id="imgf000049_0001" he="14" wi="75" file="imgf000049_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> [2]

p0250Synthetic Scheme

p0251<img id="imgf000050_0001" he="86" wi="108" file="imgf000050_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0252procedure

p0253Synthesis of the salt of 1-methyl-4 - ((E) -2- {4- [4- (2-sulfanylethyl) piperazin-1 - yl] phenyl} vinyl) pyridinium [2]

p025416 mg of compound [1] are dissolved in 10 water / ethanol mixture mL (v / v: 1/1); 60 mg (2 eq.) Of hydrate of 3- hydrochloride [bis (2-carboxyethyl) phosphino] propanoic acid dissolved in 1 ml of water and 21 mg (4 eq) of sodium bicarbonate in solution in 1 ml of water are added to the mixture. After 30 minutes stirring at 40 ° C under an inert atmosphere, the analyzes indicate that the mixture contains very predominantly the expected product [2].

p0255LC-MS analysis: LC-DAD (400-700 nm)

p0256Column: Waters XTerra MS C18 5 .mu.m (4.6 x 50) mm

p0257Mobile phase: A: water + 0.1% formic acid / B: Acetonitrile

p0258linear gradient: T (min)% A / B%: 0 min 95/5; 8 min 0/100

p0259Flow rate: 1 ml / min.

p0260Detection: UV LED Strip λ = 400-700nm

p0261Retention time t = 3.0 min. Relative purity> 90% MS (ESI +) m / z = 285 corresponds to the mass peak of monocation the expected product [2]

EXAMPLE OF COLOUR

p0263Example 1: color process - compound [1]

p0264Preparation of a composition A

p0265<img id="imgf000051_0001" he="49" wi="108" file="imgf000051_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0266Preparing a composition B

p0267Thioglycolic acid 1M

p0268Sodium hydroxide qs pH 8.5

p0269Demineralized water qs 100 g

p0270At 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).

p0271After 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.

p0272Example 2: staining method with compound [2]

p027310 mL of fresh solution of the compound [2] in the synthesis example are applied to a lock of 1 g hair of tone height 4 placed at the bottom of a bowl for 30 minutes at room temperature (the locks are turned over 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.

p0274Remanence 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.

p0275Visual observations In shampoos, there is no visible bleeding, the shampoo foam and the rinsing water are not colored

p0276The observed color is preserved and the lightening effect remains visible on the height of your hair so treated 4.

p0277Results in the L^*at^*b^* :

p0278The color of the locks before and after the 5 washes was evaluated in the

p0279L^*at^*b^* using a spectrophotometer CM 2600 KONICA MINOLTA ®, (illuminant

p0280D65).

p0281In this L^* at^* b^*, L^* represents the intensity of the color, has^* indicates the axis of green / red color and b^* axis 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 value of b^* the higher the grade is yellow. The change in coloring between the strands of hair HT4, stained and washed are measured by (.DELTA.E) using the following equation:

p0282Δ E = V (L * - L₀ *)² + (A * - a₀ *)² + (B * - b₀ * γ

p0283In this equation, L^*, at^* and B^* represent the values ​​measured before coloring and L₀^*, ao^* and bo^* represent the values ​​measured after dyeing or after coloring and shampoos. Plus the value of .DELTA.E, the greater the difference in color between HT4 locks and dyed locks is important. <img id="imgf000053_0002" he="57" wi="154" file="imgf000053_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

p0284The 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.

p0285Reflectance Results:

p0286The lightening of the compositions according to the invention and vis-à-vis afterglow successive shampoos were expressed also evaluated based on the reflectance of the hair. These reflectances are compared to the untreated reflectance of a lock of hair of tone height TH4.

p0287The reflectance is measured using a device spectrophotocolorimeter KONIKA-

p0288® MINOLTA CM 260Od and after irradiation of the hair with visible light in the wavelength range from 400 to 700 nanometers.

p0289Reflectance of the locks treated with the compound one application and after 5 shampoos

p0290• Reference

p0291- Compound 1

p0292- Compound 1-5 shampoos

p0293<img id="imgf000053_0001" he="48" wi="95" file="imgf000053_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

p0294Wavelength (nm) Reflectance of the locks treated with the compound 2 application and after 5 shampoos

p02952 2-5 shampoos

p0296<img id="imgf000054_0001" he="42" wi="122" file="imgf000054_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> oooooooooooooooo

p0297CN ^ O - CO OO O CN ^ - CO OO O CN ^ - CO OO O

p0298Wavelength (nm)

p0299We 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 visually clearer.

p0300In addition, the results show that the reflectance of the high hair strands of your 4 treated with the compositions 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.