WO2007110538A2 - Dyeing composition containing a masked thiol fluorescent colorant comprising a dimethylamino group, with an internal cationic charge, and method for lightening keratin materials using said colorant and disulphide colorants - Google Patents

Dyeing composition containing a masked thiol fluorescent colorant comprising a dimethylamino group, with an internal cationic charge, and method for lightening keratin materials using said colorant and disulphide colorants Download PDF

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WO2007110538A2
WO2007110538A2 PCT/FR2007/051004 FR2007051004W WO2007110538A2 WO 2007110538 A2 WO2007110538 A2 WO 2007110538A2 FR 2007051004 W FR2007051004 W FR 2007051004W WO 2007110538 A2 WO2007110538 A2 WO 2007110538A2
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formula
alkyl
fluorescent dye
dye
group
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PCT/FR2007/051004
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French (fr)
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WO2007110538A3 (en
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Andrew Greaves
Nicolas Daubresse
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L'oréal
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Priority claimed from FR0651035A external-priority patent/FR2898903B1/en
Priority claimed from FR0753071A external-priority patent/FR2912139B1/en
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Publication of WO2007110538A2 publication Critical patent/WO2007110538A2/en
Publication of WO2007110538A3 publication Critical patent/WO2007110538A3/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4933Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065Preparations for temporary colouring the hair, e.g. direct dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14Styryl dyes
    • C09B23/145Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes
    • A61K2800/432Direct dyes
    • A61K2800/4324Direct dyes in preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42Colour properties
    • A61K2800/43Pigments; Dyes
    • A61K2800/434Luminescent, Fluorescent; Optical brighteners; Photosensitizers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88Two- or multipart kits
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/94Involves covalent bonding to the substrate

Definitions

  • the invention relates to the dyeing of keratin materials using dimethylamino-masked thiol halide fluorescers and dimethylamino-disulfide dyes.
  • the direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triaryl methane type.
  • the colorings that result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions that bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their poor resistance to washes or perspiration.
  • keratinous fibers from conventional direct dyes does not make it possible to significantly lighten the keratin fibers.
  • a chemical bleaching process consists in treating keratin materials such as keratinous fibers, in particular the hair, by a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium.
  • This bleaching system has the disadvantage of degrading keratin materials, in particular keratin fibers, especially human fibers such as hair and alter their cosmetic properties.
  • the fibers tend to become rough, more difficult to disentangle and more fragile.
  • the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments.
  • Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique described in particular in the documents FR 2830189 and WO 2004/091473 makes it possible to respect the quality of the keratinous fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampooing.
  • direct dyes To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratin fibers, see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509;
  • direct dyes To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratin fibers, see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509;
  • disulfide dyes known for dyeing keratinous fibers are disulfide derivatives of aminothiophenol derivatives. Such dyes are described, for example, in patent FR 1156407. These dyes can be used under relatively mild conditions, in the presence of a slightly reducing medium or after a reducing pretreatment of the hair. However, these dyes may cause color turns during application.
  • the document WO 2005/097051 describes disulfide aza-imidazolium dyes for the direct dyeing of keratin fibers.
  • the object of the present invention is to provide new systems for the ⁇ loration of keratin materials, in particular human keratin fibers, especially the hair, which do not have the drawbacks of existing bleaching processes.
  • one of the aims of the present invention is to provide direct dyeing systems which make it possible to obtain lightening effects, in particular on naturally or artificially dark keratin fibers, which are stubborn in the face of successive shampoos, which do not degrade keratin fibers and which do not alter their cosmetic properties.
  • the present invention relates to a process for dyeing keratin materials, in particular keratinous fibers, in particular human fibers such as the hair, more particularly the dark hair, consisting in applying to the keratin materials a dye composition.
  • a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye thiol, chosen from the following dyes of formula (I) or (II):
  • Y represents i) an alkali metal; ii) an alkaline earth metal; iii) an ammonium group: N + F 1 R 13 R 7 R 5 or a phosphonium group: p + R ⁇ R ⁇ R ⁇ R ⁇ with R ⁇ R ⁇ R ⁇ and R ⁇ identical or different, representing an atom of hydrogen or a (C 1 -C 4 ) alkyl group; or iv) a thiol protecting group; >
  • An " represents an anionic counter-ion, it being understood that when the compound of formula (I) contains other cationic parts, it is associated with one or more anionic counter-ions making it possible to reach the electroneutrality of the formula (I).
  • Another subject of the invention is a method for dyeing keratinous materials, comprising applying in a time to said materials a dyeing composition comprising, in a suitable cosmetic medium, at least one dye fluorescent disulfide of formula (III),
  • the invention also relates to a dye composition
  • a dye composition comprising in a suitable cosmetic medium, a thiol fluorescent dye of formula (I) as defined above.
  • Another subject of the invention is a dyeing composition
  • a dyeing composition comprising, in a suitable cosmetic medium, at least one thiol fluorescent dye of formula (I) as defined above, and a reducing agent.
  • the invention also relates to new thiol fluorescent dyes of formula (I) as defined above.
  • the dyeing processes according to the invention make it possible to visibly stain dark keratin materials, in particular dark human keratin fibers, especially dark hair.
  • the process of the invention makes it possible to obtain a coloration of the keratin materials, in particular human keratinous fibers, in particular the hair, without degrading said material, which is persistent with respect to shampoos, of the common aggressions (sun, perspiration). , and other hair treatments.
  • the process of the invention also makes it possible to obtain a lightening of keratin materials such as keratinous fibers, particularly dark keratinous fibers and more particularly dark hair.
  • the lightening of the hair is evaluated by the variation of "pitch” before and after application of the compound of formula (I), (II) and (III).
  • tone is based on the classification of natural nuances, a tone separating each nuance from that which follows or immediately precedes it. This definition and the classification of natural shades is well known to professionals in the hair and published in the book “Science of hair treatment” Charles ZVIAK 1988, Ed Masson, p. 215 and 278.
  • the pitch ranges from 1 (black) to 10 (very light blonde), a unit corresponding to a tone; the higher the number, the clearer the nuance.
  • An artificially colored hair is a hair whose color has been modified by a coloring treatment, for example a coloration with direct dyes or oxidation dyes.
  • a coloring treatment for example a coloration with direct dyes or oxidation dyes.
  • the composition must, after application to hair, for example chestnut, bring to the results below.
  • the reflectance curves are then compared as a function of the wavelength, of the hair treated with the composition of the invention and of the untreated hair.
  • the curve corresponding to the treated hair must show a reflectance in the wavelength range from 500 to 700 nanometers higher than the curve corresponding to untreated hair.
  • the term "superior” means a difference of at least 0.05% reflectance, and preferably at least 0.1%. This does not prevent that there may exist in the wavelength range from 540 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable, or less than the reflectance curve corresponding to the untreated hair.
  • the wavelength where the difference is maximum between the curve of The reflectance of treated hair and untreated hair is in the wavelength range of 500 to 650 nanometers, and preferably in the wavelength range of 550 to 620 nanometers.
  • aryl or heteroaryl radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom chosen from:
  • a C 1 -C 16 preferably C 1 -C 8 , alkyl radical optionally substituted with one or more radicals chosen from hydroxyl and C 1 -C 4 alkoxy radicals;
  • C 2 (poly) -hydroxyalkoxy C 2 -C 4 , acylamino, amino substituted with two identical or different alkyl radicals, C 1 -C 4 , optionally carrying at least one hydroxyl group or both radicals may forming, with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated heterocycle optionally comprising another heteroatom which is identical or different from nitrogen;
  • a halogen atom such as chlorine, fluorine or bromine
  • a 5- or 6-membered heterocycloalkyl radical A 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4 ) alkyl radical, preferably methyl;
  • An amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group; ii) an amino group optionally substituted with one or two C 1 -C 2 alkyl radicals; 1 -Cs optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or different from nitrogen,
  • an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a C 1 -C 2 alkyl radical; a carbamoyl radical ((R) 2 N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; an alkylsulphonylamino radical (R 1 SO 2 -NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a radical; C 1 -C 4 alkyl, a phenyl radical; an aminosulphonyl radical ((R) 2 N-SO 2 -) in which the R radicals, which may be identical or different, represent
  • a polyhaloalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which are identical or different, the polyhaloalkyl group is, for example, trifluoromethyl;
  • cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the groups:
  • RCO-NR'- in which the radical R 'is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R is a C 1 -C 2 alkyl radical; amino substituted by two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 optionally substituted, saturated or unsaturated optionally at least one other heteroatom different or different from nitrogen; RCO-O- in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted 5- to 7-membered heterocyclic ring, saturated or unsaturated optionally comprising at least one other hetero
  • RO-CO- wherein the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted saturated or unsaturated 5- to 7-membered heterocyclic ring optionally comprising at least one other heteroatom different from or different from nitrogen;
  • a cyclic, heterocyclic radical or a non-aromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo or thioxo groups;
  • an "aryl” radical represents a mono or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;
  • a "diarylalkyl” radical represents a group comprising, on the same carbon atom of an alkyl group, two identical or different aryl groups, such as diphenylmethyl or 1,1-diphenylethyl;
  • heteroaryl radical represents a mono- or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium; , and of which at least one cycle 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 , phena
  • cyclic radical is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations; particularly the cyclic radical is cyclohexyl;
  • cyclic sterically hindered radical is a cyclic radical, aromatic or not, substituted or unsubstituted, hindered by steric effect or constraint, comprising from 6 to 14 members, which can be bridged, as sterically hindered radicals, mention may be made of bicyclo [1.1.0] butane, mesytyls such as 1,3,5-trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsillylphenyl and adamantyl ;
  • heterocyclic radical is a non-aromatic mono or polycyclic radical, condensed or not, containing from 5 to 22 members, containing from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium ;
  • an "alkyl radical” is a hydrocarbon radical Ci-Ci 6 linear or branched, preferably Ci-Cs;
  • alkyl radical may be substituted with one or more radicals chosen from the radicals i) hydroxy, ii) alkoxy, C r C 4 , iii) acylamino, iv) amino optionally substituted with one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom carrying them, a 5- to 7-membered heterocyl, optionally comprising another different heteroatom; or not nitrogen; v) or a quaternary ammonium group
  • R'R "R '" M " for which R', R", R '", which are identical or different, represent a
  • an "alkoxy radical” is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, preferably of CrCl 6 ;
  • an "alkylthio radical” is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, Ci-Ci 6 preferentially in dC 8 ; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above; the bounds defining the range of a range of values lie within this range of values; an "organic or inorganic acid salt” is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4 , iv) acids alkylsulfonic: Alk-S (O) 2 OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulphonic acids: Ar-
  • S (O) 2 OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid
  • an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, among which C r -C 6 alkylsulfonates: AIk-S (O) 2 O ", such as methylsulfonate or mesylate and ethyl sulfonate; iv) arylsulfonates: Ar-S (O) 2 O" as the benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; (vii) tartrate;
  • the thiol fluorescent dyes of formula (I) or (II) or disulfide (III) are compounds capable of absorbing in UV or visible radiation at a wavelength ⁇ abs of between 250 and 800 nm and capable of reemitting in the visible range at an emission wavelength ⁇ em between 400 and 800 nm.
  • thiol or disulfide fluorescent compounds of the invention are dyes capable of absorbing in the visible ⁇ abs between 400 and 800 nm and reemitting in the visible ⁇ em between 400 and 800 nm. More preferably, the thiol fluorescent dyes of formula (I), (II) or (III) are dyes capable of absorbing at an ⁇ abs of between 420 nm and 550 nm and of reemitting in the visible at an ⁇ em of between 550. and 620 nm.
  • the fluorescent compounds of the invention contain a SY function which may be in the covalent -SY or ionic -S " Y + form, depending on the nature of Y and the pH of the medium.
  • SY function which may be in the covalent -SY or ionic -S " Y + form, depending on the nature of Y and the pH of the medium.
  • a particular embodiment relates to the thiol fluorescent dyes of formula ( I) with SY function where Y represents an alkali metal.
  • Y is a protective group known to those skilled in the art such as those described in the books “Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217;
  • Y represents a protective group of the thiol function
  • Y is chosen from the following radicals:
  • Arylcarbonyl as phenylcarbonyl
  • aryl such as phenyl, dibenzosuberyl, or 1,3,5-cycloheptatrienyl
  • Optionally substituted heteroaryl including in particular cationic or non-cationic heteroaryl, comprising from 1 to 4 following heteroatoms: i) monocyclic with 5, 6 or 7 members such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl, isoxazolium thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl, 1 , 2,4-oxazolium, 1,2,4-thiadiazolyl, 1,2,4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl,
  • the two rings A, C optionally comprise a heteroatom
  • the ring B is a 5-, 6- or 7-membered particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl; optionally substituted heterocycloalkyl, optionally cationic, the heterocycloalkyl group represents in particular a saturated or partially saturated monocyclic group with 5, 6 or 7 members comprising 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl; , di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydro
  • R 'c, R' d, R ' ⁇ , R' f, R '9 and R' h identical or different, represent a hydrogen atom or a (Ci-C 4) alkyl, or else two groups R ' 9 with R' h , and / or R ' ⁇ with R' f form an oxo or thioxo group, or else R ' 9 with R' ⁇ together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3; preferentially R ' c to R' h represent a hydrogen atom; and An " represents a counterion;
  • aryl (C r C 4 ) alkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted with one or more groups chosen in particular from (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, for example methoxy, hydroxy, (C 1 -C 4 ) alkylcarbonyl, (di) (C 1 -C 4 ) (alkyl) amino such as dimethylamino;
  • heteroaryl (C r C 4 ) optionally substituted alkyl the heteroaryl group is in particular, cationic or otherwise, monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide groups such as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium, triazinyl, optionally substituted by one or more groups such as alkyl particularly methyl, advantageously (di) heteroaryl (CrC 4 ) alkyl is (di) heteroaryl methyl or (di) heteroarylethyl;
  • aryl such as phenyl optionally substituted by one or more groups such as (CrC 4 ) alkyl, (CrC 4 ) alkoxy, hydroxy; optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted with a (C 1 -C 4 ) alkyl group;
  • R ' 1 R 12 R' 3 with R ' 1 , and R' 2 identical or different represent a hydroxyl group, (C 1 -C 4 ) alkyl or alkyl, R ' 3 represents a hydroxyl group or C r C 4 ) alkoxy, and Z 1 represents an oxygen or sulfur atom;
  • Sterically hindered cyclic such as the adamantyl group
  • Optionally substituted alkoxy (CrC 4 ) alkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.
  • the protected thiol fluorescent dyes of formula (I) contain a cationic aromatic 5- or 6-membered monocyclic heterocyclic group, Y, comprising 1 to 4 heteroatoms chosen 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, tetrazinium, oxazepinium, thiepinyl, thiepinium, imidazolium; ii) cationic 8 to 11-membered bicyclic heteroaryl such as indolinium, benzoimidazolium, benzoxazolium, benzothiazolium, imidazolium
  • R ' c and R' d identical or different, represent a hydrogen atom or a group (dC 4 ) alkyl; preferentially R ' c to R' d represent a grouping
  • Y represents a group chosen 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, triazinium and imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted by one or more (CrC 4 ) alkyl groups including methyl.
  • Y represents an alkali metal or a protective group such as:> (C r C 4 ) alkylcarbonyl such as methylcarbonyl or ethylcarbonyl;
  • arylcarbonyl such as phenylcarbonyl
  • aryl such as phenyl
  • Cationic monocyclic 5- to 6-membered heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted with one or more, identical or different, (CrC 4 ) alkyl groups such as methyl;
  • fluorescent dyes of formula (I), (II) or (III) mention may be made in particular of the following compounds:
  • the protected thiol dyes of formula (I 1 ) and (I ") can be synthesized in two steps: the first step of preparing the unprotected thiol dye (II) according to methods known to those skilled in the art as per For example 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 to those skilled in the art for driving. protected thiol dyes of formula (I 1 ) and (I ").
  • thiol reagent ( ⁇ ) Y'-SH comprising a group Y 'as defined previously, whose nucleophilic function SH can react on the carbon atom alpha of the halogen atom borne by the fluorescent chromophore 7 to yield the protected thiol fluorescent dye of formula (I 1 ):
  • R ' c , R' d , HaI, An " and Gp " are as defined above.
  • a chromophore comprising another type of nucleofuge such as tosylate, mesylate or triflate.
  • an imidazoline intermediate from the halide comprising the fluorescent chromophore (a 1 ) and a thioimidazoline (b 1 ) to conduct after alkylation with a reagent R-Gp 'with R representing an alkyl group and Gp 'a leaving group such as a halogen like chlorine, bromine, iodine, or a mesylate or tosylate group with a fluorescent dye of formula (I "").
  • the protected thiol fluorescent dyes can be generated from the compound (b) and the thiol reagent comprising a leaving group Gp such that (c).
  • the leaving group may be a mesylate, tosylate, triflate or halide:
  • the protected thiol fluorescent dyes of formula (I) according to the invention can be obtained by condensation of a derivative of
  • 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 èm ⁇ Ed, John Wiley & Sons, NY , 1992.
  • Protected thiol dyes may be deprotected by conventional routes such as those described in the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005.
  • the starting reagents are commercial or accessible by conventional methods known to those skilled in the art.
  • Gp representing a leaving group nucleofuge, such as mesylate, tosylate, triflate or halide.
  • composition of the invention contains at least one thiol fluorescent dye of formula (I).
  • the composition of the invention may also contain a reducing agent.
  • This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol.
  • This reducing agent may also be chosen from borohydrides and their derivatives, for example the salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra n-butylammonium, benzyltriethylammonium); catechol borane.
  • borohydrides and their derivatives for example the salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra n-butylammonium, benzyltriethylammonium); catechol borane.
  • the dye composition useful in the invention generally contains a quantity of fluorescent dye of formula (I), (II) or (III) of between 0.001 and 50% relative to 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.
  • the dye composition may further contain additional direct dyes.
  • These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
  • the dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers.
  • oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.
  • couplers there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.
  • the coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.
  • the oxidation base (s) present in the dyeing composition are generally present each in an amount of between 0.001% and 10% by weight of the weight. total of the dyeing composition, preferably between 0.005 and 6% by weight.
  • addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates
  • a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • the medium suitable for dyeing is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent.
  • organic solvent there may be mentioned, for example lower alkanols dC 4 , such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as 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 approximately.
  • the invention contains a reducing agent capable of reducing the disulfide bonds of keratin.
  • This reducing agent is as defined above.
  • the dye composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers.
  • adjuvants conventionally used in compositions for dyeing hair such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers.
  • inorganic or organic thickeners and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, film-forming agents, ceramides, preserving agents, opacifying agents, conductive polymers.
  • the adjuvants above are generally present in an amount each of them between 0.01 and 20% by weight relative to the weight of the composition.
  • the pH of the dyeing composition is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems.
  • acidifying agents mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.
  • alkalinizing agents for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula ( ⁇ ): aj / a2
  • the dye composition may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratinous fibers, and in particular hair.
  • a reducing agent may be applied pre-treatment before the application of the composition containing at least one fluorescent dye of formula (I) or (II).
  • This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol.
  • thiols for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol.
  • This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane.
  • borohydrides and their derivatives such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane.
  • This pretreatment may be of short duration, in particular from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes with a reducing agent as mentioned above.
  • the composition comprising at least one fluorescent dye of formula (I), (II) or at least one disulfide dye of formula (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
  • the process of the invention may be preceded by a deprotection step intended to restore in situ the SH function of the dye of formula (I).
  • the deprotection step can also be carried out in the course of a hair pretreatment step such as, for example, the reducing pretreatment of the hair.
  • the reducing agent is added to the dyeing composition containing at least one fluorescent dye of formula (I), (II) or at least one dye of formula (III) at the time of use.
  • the reducing agent is applied in post-treatment, after the application of the composition containing at least one thiol fluorescent dye (I).
  • the duration of the post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above.
  • the reducing agent is a thiol or borohydride type agent as described above.
  • a particular embodiment of the invention relates to a method of directly applying a composition comprising at least one fluorescent dye of formula (I), (II) or (III).
  • the lightening-effect dyeing method does not require any pre-or post-treatment reducing agents, and consists in applying a composition comprising at least one thiol fluorescent dye of formula (I), (II) or (III ) free of reducer.
  • the dyeing process consists in applying to the keratin materials a composition comprising at least one disulfide dye of formula (III) premixed with a reducing agent as defined above.
  • Another variant of the invention relates to a dyeing method consisting in applying in a time to the keratin materials a dyeing composition comprising, in a suitable cosmetic medium, at least one disulfide fluorescent dye of formula (III); and a reducing agent.
  • the dye composition comprising at least one disulfide dye of formula (III) and the reducing agent are mixed together before application to the keratin materials just before application.
  • a treatment with an oxidizing agent may optionally be associated.
  • Any type of conventional oxidizing agent may be used in the art. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, as well as the enzymes among which may be mentioned peroxidases, oxides and the like. 2-electron reductases such as uricases and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.
  • This oxidizing agent may be applied to the fibers before or after the application of the composition containing at least one thiol 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. However, it can be carried out at temperatures ranging from 20 to 180 ° C.
  • the invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one thiol fluorescent dye of formula (I), (II) or (III) and a second compartment contains a reducing agent capable of reducing the disulfide functions of the keratin materials or the disulfide bond of the dye (III).
  • One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye.
  • a multi-compartment device in which a first compartment contains a dye composition comprising at least one fluorescent thiol dye of formula (I) or (II); a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials; a third compartment contains an oxidizing agent.
  • the dyeing device contains a first compartment containing a dye composition which comprises at least one protected thiol fluorescent dye of formula (I) and a second compartment containing an agent capable of deprotecting the protected thiol to release the thiol.
  • Each of the devices mentioned above can be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2 586 913.
  • Step 1 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4-methylpyridinium) dibromide
  • NMP N-methylpyrrolidinone
  • Step 2 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4- ⁇ (E) -2- [4- (dimethylamino) phenyl] vinyl ⁇ pyridinium dibromide [II]
  • compositions A (9 ml) and B (1 ml) are mixed, and then the mixture obtained is applied to a lock of 1 g of dark hair (pitch 4) for 30 minutes at room temperature. (The locks are returned and re-impregnated after 15 minutes).
  • the locks thus treated are divided in two, one half is subjected to 5 successive shampoos in a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water followed by drying.
  • L * a * b * L * represents the intensity of the color
  • a * indicates the green / red color axis
  • b * the blue / yellow color axis.
  • the higher the L value the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color.
  • ⁇ E The variation of the color between the locks of hair of HT 4 and the locks of hair after treatment (coloration, or coloration and successive washings) is measured by ⁇ E according to the following equation:
  • L *, a * and b * represent the values measured after treatment and L 0 *, ao * and bo * represent the values measured before treatment.
  • compositions according to the invention were expressed as a function of the reflectance of the hair. These reflectances are compared to the reflectance of an untreated strand of HT4 pitch hair.
  • the reflectance is measured using a KONIKA-MINOLTA®, CM 260Od spectrophotocolorimeter and after irradiation of the hair with visible light in the wavelength range of 400 to 700 nanometers.

Abstract

The invention relates to a dyeing composition comprising a masked thiol fluorescent colorant having a dimethylamino group, and to a method for colouring keratin materials, especially keratin fibres, particularly human keratin fibres such as hair, with a lightening effect, using said composition or a composition comprising at least one disulphide colorant having a dimethylamino group in the presence of a reducer. The invention also relates to novel thiol fluorescent colorants and the uses thereof for lightening keratin materials. Said composition produces a lightening effect which is especially tenacious and visible on dark keratin fibres.

Description

COMPOSITION DE TEINTURE COMPRENANT UN COLORANT FLUORESCENT DYE COMPOSITION COMPRISING A FLUORESCENT COLOR
THIOL MASQUE A GROUPE DIMETHYLAMINO, A CHARGE CATIONIQUE INTERNE, PROCEDE D'ECLAIRCISSEMENT DES MATIERES KERATINIQUES ATHIOL DIMETHYLAMINO GROUP MASK WITH INTERNAL CATIONIC LOAD, METHOD OF CLEARING KERATINIC MATERIALS
PARTIR DE CE COLORANT ET DE COLORANT DISUFUREFROM THIS DYE AND COLOR DISEFURE
L'invention concerne la coloration de matières kératiniques à l'aide de colorants fluorescents thiols masqué à groupe diméthylamino, et à colorant disulfure à groupe diméthylamino.The invention relates to the dyeing of keratin materials using dimethylamino-masked thiol halide fluorescers and dimethylamino-disulfide dyes.
Il est connu de teindre les fibres kératiniques, notamment humaines, par une coloration directe. Le procédé classiquement utilisé en coloration directe consiste à appliquer sur les fibres kératiniques des colorants directs qui sont des molécules colorées et colorantes ayant une affinité pour les fibres, à les laisser diffuser, puis à rincer les fibres.It is known to dye keratinous fibers, especially human fibers, by direct dyeing. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyeing molecules having an affinity for the fibers, allowing them to diffuse and then rinsing the fibers.
Les colorants directs qui sont classiquement utilisés sont par exemple des colorants du type nitrés benzéniques, des colorants anthraquinoniques, des nitropyridines, des colorants du type azoïque, xanthénique, acridinique, azinique ou triaryl méthane.The direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triaryl methane type.
Les colorations qui résultent de l'utilisation de colorants directs sont des colorations temporaires ou semi-permanentes car la nature des interactions qui lient les colorants directs à la fibre kératinique, et leur désorption de la surface et/ou du cœur de la fibre sont responsables de leur faible puissance tinctoriale et de leur mauvaise tenue aux lavages ou à la transpiration.The colorings that result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions that bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their poor resistance to washes or perspiration.
Par ailleurs, la coloration des fibres kératiniques à partir de colorants directs classiques ne permet pas d'éclaircir de façon notable les fibres kératiniques. L'éclaircissement de la couleur de fibres kératiniques, plus particulièrement foncées vers des nuances plus claires, en modifiant éventuellement la nuance de celles-ci, constitue une demande importante.Furthermore, the coloration of keratinous fibers from conventional direct dyes does not make it possible to significantly lighten the keratin fibers. The lightening of the color of keratinous fibers, more particularly dark to lighter shades, possibly modifying the shade of these, constitutes an important demand.
Classiquement, pour obtenir une coloration plus claire on met en œuvre un procédé de décoloration chimique. Ce procédé consiste à traiter les matières kératiniques telles que les fibres kératiniques, notamment les cheveux, par un système oxydant fort, généralement constitué par du peroxyde d'hydrogène associé ou non à des persels, le plus souvent en milieu alcalin.Conventionally, to obtain a lighter coloration is implemented a chemical bleaching process. This method consists in treating keratin materials such as keratinous fibers, in particular the hair, by a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium.
Ce système de décoloration présente l'inconvénient de dégrader des matières kératiniques, en particulier les fibres kératiniques, notamment humaines telles que les cheveux et d'altérer leurs propriétés cosmétiques. Les fibres ont en effet tendance à devenir rêches, plus difficilement démêlables et plus fragiles. Enfin, l'éclaircissement ou la décoloration de fibres kératiniques par des agents oxydants est incompatible avec les traitements de modification de la forme desdites fibres particulièrement dans les traitements de défrisage.This bleaching system has the disadvantage of degrading keratin materials, in particular keratin fibers, especially human fibers such as hair and alter their cosmetic properties. The fibers tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments.
Une autre technique d'éclaircissement consiste à appliquer sur les cheveux foncés des colorants directs fluorescents. Cette technique décrite notamment dans les documents FR 2830189 et WO 2004/091473 permet de respecter la qualité de la fibre kératinique lors du traitement mais les colorants fluorescents employés ne présentent pas une résistance aux shampoings satisfaisante.Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique described in particular in the documents FR 2830189 and WO 2004/091473 makes it possible to respect the quality of the keratinous fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampooing.
Pour augmenter la ténacité des colorations directes, il est connu de fixer des colorants directs par liaison covalente au cheveu. Par exemple, il est connu de faire réagir des colorants à groupements réactifs avec les résidus de cystine ou de cystéine très nombreux dans les fibres kératiniques voir par exemple Journal of the Society of Dyers and Colourists, Guise et Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509;To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratin fibers, see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509;
De plus il est connu de protéger la ou les fonctions thiols contenues dans une molécule à greffer aux cheveux avant de les appliquer auxdits cheveux WO 99/51194. Cependant cette demande ne mentionne pas l'utilisation de colorants fluorescents permettant de colorer ou d'éclaircir des cheveux.In addition, it is known to protect the thiol function (s) contained in a molecule to be grafted to the hair before being applied to said hair WO 99/51194. However, this application does not mention the use of fluorescent dyes for coloring or lightening hair.
Pour augmenter la ténacité des colorations directes, il est connu de fixer des colorants directs par liaison covalente au cheveu. Par exemple, il est connu de faire réagir des colorants à groupements réactifs avec les résidus de cystine ou de cystéine très nombreux dans les fibres kératiniques voir par exemple Journal of the Society of Dyers and Colourists, Guise et Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509;To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratin fibers, see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509;
D'autres colorants disulfures connus pour la coloration des fibres kératiniques sont des dérivés disulfures de dérivés d'aminothiophénol. De tels colorants sont décrits par exemple dans le brevet FR 1156407. Ces colorants peuvent être utilisés dans des conditions relativement douces, en présence d'un milieu légèrement réducteur ou après un pré-traitement réducteur du cheveu. Cependant, ces colorants peuvent occasionner des virages de couleur lors de l'application.Other disulfide dyes known for dyeing keratinous fibers are disulfide derivatives of aminothiophenol derivatives. Such dyes are described, for example, in patent FR 1156407. These dyes can be used under relatively mild conditions, in the presence of a slightly reducing medium or after a reducing pretreatment of the hair. However, these dyes may cause color turns during application.
Enfin, le document WO 2005/097051 décrit des colorants disulfures aza- imidazoliums pour la coloration directe de fibres kératiniques. Le but de la présente invention est de fournir de nouveaux systèmes de ∞loration de matières kératiniques en particulier les fibres kératiniques humaines, notamment les cheveux, qui ne présentent pas les inconvénients des procédés de décoloration existants. En particulier, un des buts de la présente invention est de fournir des systèmes de coloration directe permettant d'obtenir des effets éclaircissants notamment sur des fibres kératiniques naturellement ou artificiellement foncées, tenaces face à des shampooings successifs, qui ne dégradent pas les fibres kératiniques et qui n'altèrent pas leurs propriétés cosmétiques.Finally, the document WO 2005/097051 describes disulfide aza-imidazolium dyes for the direct dyeing of keratin fibers. The object of the present invention is to provide new systems for the ∞loration of keratin materials, in particular human keratin fibers, especially the hair, which do not have the drawbacks of existing bleaching processes. In particular, one of the aims of the present invention is to provide direct dyeing systems which make it possible to obtain lightening effects, in particular on naturally or artificially dark keratin fibers, which are stubborn in the face of successive shampoos, which do not degrade keratin fibers and which do not alter their cosmetic properties.
Ce but est atteint avec la présente invention qui a pour objet un procédé de coloration de matières kératiniques, en particulier les fibres kératiniques, notamment humaines telles que les cheveux, plus particulièrement les cheveux foncés, consistant à appliquer sur les matières kératiniques, une composition tinctoriale, comprenant dans un milieu cosmétique approprié, au moins un colorant fluorescent thiol, choisi parmi les colorants de formule (I) ou (II) suivante :This object is achieved with the present invention which relates to a process for dyeing keratin materials, in particular keratinous fibers, in particular human fibers such as the hair, more particularly the dark hair, consisting in applying to the keratin materials a dye composition. comprising, in a suitable cosmetic medium, at least one fluorescent dye thiol, chosen from the following dyes of formula (I) or (II):
Figure imgf000004_0001
leurs sels d'acide organique ou minéral, isomères optiques, isomères géométriques, et les solvates tels que hydrates ;
Figure imgf000004_0001
their organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates;
formules (I) ou (II) dans lesquelles : > Y représente i) un métal alcalin ; ii) un métal alcalino-terreux ; iii) un groupement ammonium : N+F^R13R7R5 ou un groupement phosphonium : p+RαR β R γ R δ avec Rα R β R γ et R δ identiques ou différents, représentant un atome d'hydrogène ou un groupe (Ci-C4)alkyle ; ou iv) un groupement protecteur de fonction thiol ; > An" représente un contre-ion anionique ; étant entendu que lorsque le composé de formule (I) contient d'autres parties cationiques, il se trouve associé à un ou plusieurs contre-ions anioniques permettant d'atteindre l'électroneutralité de la formule (I).formulas (I) or (II) wherein:> Y represents i) an alkali metal; ii) an alkaline earth metal; iii) an ammonium group: N + F 1 R 13 R 7 R 5 or a phosphonium group: p + R α R β R γ R δ with R α R β R γ and R δ identical or different, representing an atom of hydrogen or a (C 1 -C 4 ) alkyl group; or iv) a thiol protecting group; > An " represents an anionic counter-ion, it being understood that when the compound of formula (I) contains other cationic parts, it is associated with one or more anionic counter-ions making it possible to reach the electroneutrality of the formula (I).
Un autre objet de l'invention est un procédé de coloration de matières kératiniques consistant à appliquer en un temps sur lesdites matières une composition tinctoriale, comprenant dans un milieu cosmétique approprié, au moins un colorant fluorescent disulfure de formule (III),Another subject of the invention is a method for dyeing keratinous materials, comprising applying in a time to said materials a dyeing composition comprising, in a suitable cosmetic medium, at least one dye fluorescent disulfide of formula (III),
Figure imgf000005_0001
Figure imgf000005_0001
ses sels d'acide organique ou minéral, isomères optiques, isomères géométriques, et les solvates tels que hydrates ; formule (III) dans laquelle An" représente un contre-ion anionique ; et un agent réducteur.its organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formula (III) wherein An " represents an anionic counterion, and a reducing agent.
L'invention a également pour objet une composition tinctoriale comprenant dans un milieu cosmétique approprié, un colorant fluorescent thiol de formule (I) tel que défini précédemment.The invention also relates to a dye composition comprising in a suitable cosmetic medium, a thiol fluorescent dye of formula (I) as defined above.
Un autre objet de l'invention est une composition tinctoriale comprenant, dans un milieu cosmétique approprié au moins un colorant fluorescent thiol de formule (I) tels que définis précédemment, et un agent réducteur.Another subject of the invention is a dyeing composition comprising, in a suitable cosmetic medium, at least one thiol fluorescent dye of formula (I) as defined above, and a reducing agent.
L'invention a aussi pour objet de nouveaux colorants fluorescents thiols de formule (I) tel que défini précédemment.The invention also relates to new thiol fluorescent dyes of formula (I) as defined above.
Les procédés de coloration selon l'invention permettent de colorer de façon visible les matières kératiniques foncées, en particulier les fibres kératiniques humaines foncées, notamment les cheveux foncés.The dyeing processes according to the invention make it possible to visibly stain dark keratin materials, in particular dark human keratin fibers, especially dark hair.
De plus le procédé de l'invention permet d'obtenir une coloration des matières kératiniques en particulier les fibres kératiniques humaines, notamment les cheveux, sans dégrader ladite matière, rémanente vis-à-vis de shampooings, des agressions courantes (soleil, transpiration), et des autres traitements capillaires. Le procédé de l'invention permet également d'obtenir un éclaircissement des matières kératiniques telles que les fibres kératiniques particulièrement les fibres kératiniques foncées et plus particulièrement les cheveux foncés.In addition, the process of the invention makes it possible to obtain a coloration of the keratin materials, in particular human keratinous fibers, in particular the hair, without degrading said material, which is persistent with respect to shampoos, of the common aggressions (sun, perspiration). , and other hair treatments. The process of the invention also makes it possible to obtain a lightening of keratin materials such as keratinous fibers, particularly dark keratinous fibers and more particularly dark hair.
Au sens de l'invention, on entend par matière kératinique foncée celle qui présente une luminescence L* chiffrée dans le système C. I. E. L*a*b*, inférieure ou égale à 45 et de préférence inférieure ou égale à 40, sachant par ailleurs que L*=0 équivaut au noir et L*=100 au blanc. Au sens de l'invention, on entend par cheveux naturellement ou artificiellement foncés, des cheveux dont la hauteur de ton est inférieure ou égale à 6 (blond foncé) et de préférence inférieure ou égale à 4 (châtain).For the purposes of the invention, the term "dark keratin material" is understood to mean that which has an enumerated luminescence L * in the CIE system L * a * b *, less than or equal to 45 and preferably less than or equal to 40, while also knowing that L * = 0 is equivalent to black and L * = 100 is white. For the purposes of the invention, the term hair naturally or artificially dark, hair whose pitch is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut).
L'éclaircissement des cheveux est évalué par la variation de « hauteur de ton » avant et après application du composé de formule (I), (II) et (III). La notion « ton » repose sur la classification des nuances naturelles, un ton séparant chaque nuance de celle qui la suit ou la précède immédiatement. Cette définition et la classification des nuances naturelles est bien connue des professionnels de la coiffure et publiée dans l'ouvrage « Science des traitement capillaires » de Charles ZVIAK 1988, Ed. Masson, p. 215 et 278. Les hauteurs de ton s'échelonnent de 1 (noir) à 10 (blond très clair), une unité correspondant à un ton ; plus le chiffre est élevé et plus la nuance est claire.The lightening of the hair is evaluated by the variation of "pitch" before and after application of the compound of formula (I), (II) and (III). The notion "tone" is based on the classification of natural nuances, a tone separating each nuance from that which follows or immediately precedes it. This definition and the classification of natural shades is well known to professionals in the hair and published in the book "Science of hair treatment" Charles ZVIAK 1988, Ed Masson, p. 215 and 278. The pitch ranges from 1 (black) to 10 (very light blonde), a unit corresponding to a tone; the higher the number, the clearer the nuance.
Un cheveu coloré artificiellement est un cheveu dont la couleur a été modifiée par un traitement de coloration par exemple une coloration avec des colorants directs ou des colorants d'oxydation. De préférence, la composition doit, après application sur des cheveux, par exemple châtains, amener aux résultats ci-dessous.An artificially colored hair is a hair whose color has been modified by a coloring treatment, for example a coloration with direct dyes or oxidation dyes. Preferably, the composition must, after application to hair, for example chestnut, bring to the results below.
On s'intéresse aux performances de réflectance des cheveux lorsqu'on les irradie avec de la lumière visible dans la gamme de longueurs d'onde allant de 400 à 700 nanomètres. - On compare alors les courbes de réflectance en fonction de la longueur d'onde, des cheveux traités avec la composition de l'invention et des cheveux non traités. - La courbe correspondant aux cheveux traités doit montrer une réflectance dans la gamme des longueurs d'onde allant de 500 à 700 nanomètres supérieure à la courbe correspondant aux cheveux non traités. - Cela signifie que, dans la gamme de longueur d'onde allant de 540 à 700 nanomètres, il existe au moins une plage où la courbe de réflectance correspondant aux cheveux traités est supérieure à la courbe de réflectance correspondant aux cheveux non traités. On entend par "supérieure", un écart d'au moins 0,05% de réflectance, et de préférence d'au moins 0,1%. Ceci n'empêche pas qu'il peut exister dans la gamme de longueur d'onde allant de 540 à 700 nanomètres, au moins une plage où la courbe de réflectance correspondant aux cheveux traités soit superposable, ou inférieure à la courbe de réflectance correspondant aux cheveux non traités.We are interested in the reflectance performance of hair when irradiated with visible light in the wavelength range of 400 to 700 nanometers. The reflectance curves are then compared as a function of the wavelength, of the hair treated with the composition of the invention and of the untreated hair. - The curve corresponding to the treated hair must show a reflectance in the wavelength range from 500 to 700 nanometers higher than the curve corresponding to untreated hair. This means that, in the wavelength range of 540 to 700 nanometers, there is at least one range where the reflectance curve corresponding to the treated hair is greater than the reflectance curve corresponding to the untreated hair. The term "superior" means a difference of at least 0.05% reflectance, and preferably at least 0.1%. This does not prevent that there may exist in the wavelength range from 540 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable, or less than the reflectance curve corresponding to the untreated hair.
De préférence, la longueur d'onde où l'écart est maximal entre la courbe de réflectance des cheveux traités et celle des cheveux non traités, se situe dans la gamme de longueur d'onde allant de 500 à 650 nanomètres, et de préférence dans la gamme de longueur d'onde allant de 550 à 620 nanomètres.Preferably, the wavelength where the difference is maximum between the curve of The reflectance of treated hair and untreated hair is in the wavelength range of 500 to 650 nanometers, and preferably in the wavelength range of 550 to 620 nanometers.
Au sens de la présente invention, et à moins qu'une indication différente ne soit donnée :For the purposes of the present invention, and unless a different indication is given:
- les radicaux « aryle » ou « hétéroaryle » ou la partie aryle ou hétéroaryle d'un radical peuvent être substitués par au moins un substituant porté par un atome de carbone, choisi parmi :the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom chosen from:
. un radical alkyle en C1-C16, de préférence en C1-C8, éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux hydroxy, alcoxy en C1-. a C 1 -C 16 , preferably C 1 -C 8 , alkyl radical optionally substituted with one or more radicals chosen from hydroxyl and C 1 -C 4 alkoxy radicals;
C2, (poly)-hydroxyalcoxy en C2-C4, acylamino, amino substitué par deux radicaux alkyle, identiques ou différents, en C1-C4 , éventuellement porteurs d'au moins un groupement hydroxy ou, les deux radicaux pouvant former avec l'atome d'azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, de préférence de 5 ou 6 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement un autre hétéroatome identique ou différent de l'azote ;C 2 , (poly) -hydroxyalkoxy C 2 -C 4 , acylamino, amino substituted with two identical or different alkyl radicals, C 1 -C 4 , optionally carrying at least one hydroxyl group or both radicals may forming, with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated heterocycle optionally comprising another heteroatom which is identical or different from nitrogen;
. un atome d'halogène tel que chlore, fluor ou brome ;. a halogen atom such as chlorine, fluorine or bromine;
• un groupement hydroxy ; . un radical alcoxy en C1-C2 ;• a hydroxyl group; . a C 1 -C 2 alkoxy radical;
• un radical alkylthio en C1-C2 ;A C 1 -C 2 alkylthio radical;
. un radical (poly)-hydroxyalcoxy en C2-C4 ;. a (C 2 -C 4 ) polyhydroxyalkoxy radical;
• un radical amino ;An amino radical;
. un radical héterocycloalkyle à 5 ou 6 chaînons ; • un radical hétéroaryle à 5 ou 6 chaînons éventuellement cationique, préférentiellement imidazolium, et éventuellement substitué par un radical (C1-C4) alkyle, préférentiellement méthyle ;. a 5- or 6-membered heterocycloalkyl radical; A 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4 ) alkyl radical, preferably methyl;
• un radical amino substitué par un ou deux radicaux alkyle, identiques ou différents, en C1-C6 éventuellement porteurs d'au moins : i) un groupement hydroxy, ii) un groupement amino éventuellement substituté par un ou deux radicaux alkyle en C1-Cs éventuellement substitués, lesdits radicaux alkyle pouvant former avec l'atome d'azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement au moins un autre hétéroatome différent ou non de l'azote,An amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group; ii) an amino group optionally substituted with one or two C 1 -C 2 alkyl radicals; 1 -Cs optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or different from nitrogen,
. un radical acylamino (-NR-COR') dans lequel le radical R est un atome d'hydrogène, un radical alkyle en CrC4 éventuellement porteur d'au moins un groupement hydroxy et le radical R' est un radical alkyle en CrC2 ; un radical carbamoyle ((R)2N-CO-) dans lequel les radicaux R, identiques ou non, représentent un atome d'hydrogène, un radical alkyle en C1-C4 éventuellement porteur d'au moins un groupement hydroxy ; un radical alkylsulfonylamino (R1SO2-NR-) dans lequel le radical R représente un atome d'hydrogène, un radical alkyle en C1-C4 éventuellement porteur d'au moins un groupement hydroxy et le radical R' représente un radical alkyle en C1-C4, un radical phényle ; un radical aminosulfonyle ((R)2N-SO2-) dans lequel les radicaux R, identiques ou non, représentent un atome d'hydrogène, un radical alkyle en C1-C4 éventuellement porteur d'au moins un groupement hydroxy, • un radical carboxylique sous forme acide ou salifiée (de préférence avec un métal alcalin ou un ammonium, substitué ou non) ;. an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is a C 1 -C 2 alkyl radical; a carbamoyl radical ((R) 2 N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; an alkylsulphonylamino radical (R 1 SO 2 -NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a radical; C 1 -C 4 alkyl, a phenyl radical; an aminosulphonyl radical ((R) 2 N-SO 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group, A carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);
• un groupement cyano ;• a cyano group;
. un groupement polyhalogénoalkyle comprenant de 1 à 6 atomes de carbones et de 1 à 6 atome d'halogène, identiques ou différents, le groupement polyhalogénoalkyle est par exemple le trifluorométhyle ;. a polyhaloalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which are identical or different, the polyhaloalkyl group is, for example, trifluoromethyl;
- la partie cyclique ou hétérocyclique d'un radical non aromatique peut être substituée par au moins un substituant porté par un atome de carbone choisi parmi les groupements :the cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the groups:
. hydroxy, • alcoxy en C1-C4,. hydroxy, • C 1 -C 4 alkoxy,
. (poly)hydroxyalcoxy en C2-C4,. (poly) hydroxyalkoxy C 2 -C 4 ,
• un radical alkylthio en C1-C2 ;A C 1 -C 2 alkylthio radical;
. RCO-NR'- dans lequel le radical R' est un atome d'hydrogène, un radical alkyle en C1-C4 éventuellement porteur d'au moins un groupement hydroxy et le radical R est un radical alkyle en C1-C2, amino substitué par deux groupements alkyle identiques ou différents en C1-C4 éventuellement porteurs d'au moins un groupement hydroxy, lesdits radicaux alkyle pouvant former avec l'atome d'azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement au moins un autre hétéroatome différent ou non de l'azote ; • RCO-O- dans lequel le radical R est un radical alkyle en CrC4, amino substitué par deux groupements alkyle identiques ou différents en CrC4 éventuellement porteurs d'au moins un groupement hydroxy, lesdits radicaux alkyle pouvant former avec l'atome d'azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement au moins un autre hétéroatome différent ou non de l'azote ; . RO-CO- dans lequel le radical R est un radical alkyle en C1-C4, amino substitué par deux groupements alkyle identiques ou différents en C1-C4 éventuellement porteurs d'au moins un groupement hydroxy, lesdits radicaux alkyle pouvant former avec l'atome d'azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement au moins un autre hétéroatome différent ou non de l'azote ;. RCO-NR'- in which the radical R 'is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R is a C 1 -C 2 alkyl radical; amino substituted by two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 optionally substituted, saturated or unsaturated optionally at least one other heteroatom different or different from nitrogen; RCO-O- in which the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted 5- to 7-membered heterocyclic ring, saturated or unsaturated optionally comprising at least one other heteroatom different or different from nitrogen; . RO-CO- wherein the radical R is a C 1 -C 4 alkyl radical, amino substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, an optionally substituted saturated or unsaturated 5- to 7-membered heterocyclic ring optionally comprising at least one other heteroatom different from or different from nitrogen;
- un radical cyclique, hétérocyclique, ou une partie non aromatique d'un radical aryle ou hétéroaryle, peut également être substitué par un ou plusieurs groupements oxo ou thioxo ;a cyclic, heterocyclic radical or a non-aromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo or thioxo groups;
- un radical « aryle » représente un groupement mono ou polycyclique, condensé ou non, comprenant de 6 à 22 atomes de carbones, et dont au moins un cycle est aromatique ; préférentiellement le radical aryle est un phényle, biphényle, naphtyle, indényle, anthracényle, ou tétrahydronaphtyle ;an "aryl" radical represents a mono or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;
- un radical « diarylalkyle » représente un groupement comportant sur le même atome de carbone d'un groupement alkyle deux groupement aryle, identiques ou différents tel que diphénylméthyle ou 1,1-diphényléthyle ;a "diarylalkyl" radical represents a group comprising, on the same carbon atom of an alkyl group, two identical or different aryl groups, such as diphenylmethyl or 1,1-diphenylethyl;
- un « radical hétéroaryle » représente un groupement mono ou polycyclique, condensé ou non, éventuellement cationique, comprenant de 5 à 22 chaînons, de 1 à 6 hétéroatomes choisis parmi l'atome d'azote, d'oxygène, de soufre et de sélénium, et dont au moins un cycle est aromatique ; préférentiellement un radical hétéroaryle est choisis parmi acridinyle, benzimidazolyle, benzobistriazolyle, benzopyrazolyle, benzopyridazinyle, benzoquinolyle, benzothiazolyle, benzotriazolyle, benzoxazolyle, pyridinyle, tétrazolyle, dihydrothiazolyle, imidazopyridinyle, imidazolyle, indolyle, isoquinolyle, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyle, oxazolyle, oxazolopyridyle, phénazinyle, phénooxazolyle, pyrazinyle, pyrazolyle, pyrilyle, pyrazoyltriazyle, pyridyle, pyridinoimidazolyle, pyrrolyle, quinolyle, tétrazolyle, thiadiazolyle, thiazolyle, thiazolopyridinyle, thiazoylimidazolyle, thiopyrylyle, triazolyle, xanthylyle et son sel d'ammonium ; - un radical « dihétéroarylalkyle » représente un groupement comportant sur le même atome de carbone d'un groupement alkyle deux groupement hétéroaryle, identiques ou différents tel que difurylméthyle, 1 ,1-difuryléthyle, dipyrrolylméthyle, dithiénylméthyle ;a "heteroaryl radical" represents a mono- or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium; , and of which at least one cycle 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, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyryl, triazolyl, xanthylyl and its ammonium salt; a "diheteroarylalkyl" radical represents a group comprising, on the same carbon atom of an alkyl group, two heteroaryl groups, identical or different, such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl, dithienylmethyl;
- un « radical cyclique » est un radical cycloalkyle non aromatique, mono ou polycyclique, condensé ou non, contenant de 5 à 22 atomes de carbone, pouvant comporter de 1 à plusieurs insaturations ; particulièrement le radical cyclique est un cyclohexyle ;a "cyclic radical" is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations; particularly the cyclic radical is cyclohexyl;
- un radical « cyclique stériquement encombré» est un radical cyclique, aromatique ou non, substitué ou non, encombré par effet ou contrainte stérique, comprenant de 6 à 14 chaînons, pouvant être pontés, à titre de radicaux stériquement encombrés on peut citer le bicyclo[1.1.0]butane, les mésytyles tels que le 1 ,3,5- triméthylpnényle, le 1,3,5-triterbutylphényle, le 1 ,3,5-isobutylphényle, le 1,3,5- trimétylsillylphényle et l'adamantyle ;a "cyclic sterically hindered" radical is a cyclic radical, aromatic or not, substituted or unsubstituted, hindered by steric effect or constraint, comprising from 6 to 14 members, which can be bridged, as sterically hindered radicals, mention may be made of bicyclo [1.1.0] butane, mesytyls such as 1,3,5-trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsillylphenyl and adamantyl ;
- un « radical hétérocyclique » est un radical non aromatique mono ou polycyclique, condensé ou non, contenant de 5 à 22 chaînons, comportant de 1 à 6 hétéroatomes choisis parmi l'atome d'azote, d'oxygène, de soufre et de sélénium ;a "heterocyclic radical" is a non-aromatic mono or polycyclic radical, condensed or not, containing from 5 to 22 members, containing from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium ;
- un « radical alkyle » est un radical hydrocarboné en Ci-Ci6, linéaire ou ramifié, de préférence en Ci-Cs ;- an "alkyl radical" is a hydrocarbon radical Ci-Ci 6 linear or branched, preferably Ci-Cs;
- l'expression « éventuellement substitué » attribué au radical alkyle sous entend que ledit radical alkyle peut être substitué par un ou plusieurs radicaux choisis parmi les radicaux i) hydroxy, ii) alcoxy en CrC4, iii) acylamino, iv) amino éventuellement substitué par un ou deux radicaux alkyle, identiques ou différents, en C1-C4, lesdits radicaux alkyles pouvant former avec l'atome d'azote qui les portent un hétérocyle comprenant de 5 à 7 chaînons, comprenant éventuellement un autre hétéroatome différent ou non de l'azote ; v) ou un groupement ammonium quaternairethe expression "optionally substituted" ascribed to the alkyl radical, meaning that said alkyl radical may be substituted with one or more radicals chosen from the radicals i) hydroxy, ii) alkoxy, C r C 4 , iii) acylamino, iv) amino optionally substituted with one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom carrying them, a 5- to 7-membered heterocyl, optionally comprising another different heteroatom; or not nitrogen; v) or a quaternary ammonium group
-N R'R"R'", M" pour lequel R', R", R'", identiques ou différents représentent un-N R'R "R '", M " for which R', R", R '", which are identical or different, represent a
+ atome d'hydrogène, ou un groupement alkyle en d-C4, ou alors -N R'R"R'" forme un hétéroaryle tel que imidazolium éventuellement substitué par un groupement Cr C4 alkyle, et M représente le contre-ion de l'acide organique, minéral ou de l'halogénure correspondant,+ hydrogen atom, or a dC 4 alkyl group, or else -N R'R "R '" forms a heteroaryl such as imidazolium optionally substituted with a group C r C 4 alkyl, and M represents the counter-ion of the organic acid, mineral or corresponding halide,
- un « radical alcoxy » est un radical alkyle-oxy ou alkyl-O- pour lequel le radical alkyle est un radical hydrocarboné, linéaire ou ramifié, en CrCi6 préférentiellement ;an "alkoxy radical" is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, preferably of CrCl 6 ;
- un « radical alkylthio » est un radical alkyl-S- pour lequel le radical alkyle est un radical hydrocarboné, linéaire ou ramifié, en Ci-Ci6 préférentiellement en d-C8 ; lorsque le groupement alkylthio est éventuellement substitué, cela sous entend que le groupe alkyle est éventuellement substitué tel que défini précédemment ; les bornes délimitant l'étendue d'une plage de valeurs sont comprises dans cette plage de valeurs ; un « sel d'acide organique ou minéral » est plus particulièrement choisi parmi un sel dérivé i) d'acide chlorhydrique HCI, ii) d'acide bromhydrique HBr, iii) d'acide sulfurique H2SO4, iv) d'acides alkylsulfoniques : AIk-S(O)2OH tels que d'acide méthylsulfonique et d'acide éthylsulfonique ; v) d'acides arylsulfoniques : Ar-an "alkylthio radical" is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, Ci-Ci 6 preferentially in dC 8 ; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above; the bounds defining the range of a range of values lie within this range of values; an "organic or inorganic acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4 , iv) acids alkylsulfonic: Alk-S (O) 2 OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulphonic acids: Ar-
S(O)2OH tel que d'acide benzène sulfonique et d'acide toluène sulfonique ; vi) d'acide citrique ; vii) d'acide succinique ; viii) d'acide tartrique ; ix) d'acide lactique, x) d'acides alcoxysulfiniques : AIk-O-S(O)OH tels que d'acide méthoxysulfinique et d'acide éthoxysulfinique ; xi) d'acides aryloxysulfiniques tels que d'acide toluèneoxysulfinique et d'acide phénoxysulfinique ; xii) d'acide phosphoriqueS (O) 2 OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid
H3PO4; xiii) d'acide acétique CH3COOH ; xiv) d'acide triflique CF3SO3H et xv) d'acide tétrafluoroborique HBF4 ; un « contre-ion anionique » est un anion ou un groupement anionique associé à la charge cationique du colorant ; plus particulièrement le contre-ion anionique est choisi parmi i) les halogénures tels que le chlorure, le bromure ; ii) les nitrates ; iii) les sulfonates parmi lesquels les CrC6 alkylsulfonates : AIk-S(O)2O" tels que le méthylsulfonate ou mésylate et l'éthylsulfonate ; iv) les arylsulfonates : Ar-S(O)2O" tel que le benzènesulfonate et le toluènesulfonate ou tosylate ; v) le citrate ; vi) le succinate ; vii) le tartrate ; viii) le lactate ; ix) les alkylsulfites : AIk-O-S(O)O" tels que le méthysulfite et l'éthylsulfite ; x) les arylsulfites : Ar-O-S(O)O" tels que le benzènesulfite et le toluènesulfite ; xi) les alkylsulfates : AIk-O-S(O)2O" tel que le méthyl sulfate et l'éthylsulfate ; xii) les arylsulfates : Ar-O-S(O)2O", xiii) le phosphate ; xiv) l'acétate ; xv) le triflate ; et xvi) les borates tels que le tétrafluoroborate.H 3 PO 4 ; xiii) acetic acid CH 3 COOH; xiv) triflic acid CF 3 SO 3 H and xv) tetrafluoroboric acid HBF 4 ; an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the dye; more particularly the anionic counterion is selected from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, among which C r -C 6 alkylsulfonates: AIk-S (O) 2 O ", such as methylsulfonate or mesylate and ethyl sulfonate; iv) arylsulfonates: Ar-S (O) 2 O" as the benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; (vii) tartrate; viii) lactate; ix) alkylsulfites: Alk-OS (O) O "such as méthysulfite and éthylsulfite; x) arylsulfites: Ar-OS (O) O" such as benzènesulfite and toluènesulfite; xi) alkyl sulfates: AIk-OS (O) 2 O ", such as methyl sulphate and ethyl sulphate; xii) aryl sulfates: Ar-OS (O) 2 O", xiii) phosphate; (xiv) acetate; xv) triflate; and (xvi) borates such as tetrafluoroborate.
Les colorants fluorescents thiols de formule (I) ou (II) ou disulfure (III) sont des composés capables d'absorber dans le rayonnement UV ou visible à une longueur d'onde λabs comprise entre 250 et 800 nm et capables de réémettrent dans le domaine du visible à une longueur d'onde d'émission λém comprise entre 400 et 800 nm.The thiol fluorescent dyes of formula (I) or (II) or disulfide (III) are compounds capable of absorbing in UV or visible radiation at a wavelength λ abs of between 250 and 800 nm and capable of reemitting in the visible range at an emission wavelength λ em between 400 and 800 nm.
De préférence les composés fluorescents thiols ou disulfure de l'invention sont des colorants capables d'absorber dans le visible λabs comprise entre 400 et 800 nm et de réémettre dans le visible λém comprise entre 400 et 800 nm. Plus préférentiellement les colorants fluorescents thiols de formule (I), (II) ou (III) sont des colorants capables d'absorber à une λabs comprise entre 420 nm et 550 nm et de réémettre dans le visible à une λém comprise entre 550 et 620 nm.Preferably, thiol or disulfide fluorescent compounds of the invention are dyes capable of absorbing in the visible λ abs between 400 and 800 nm and reemitting in the visible λ em between 400 and 800 nm. More preferably, the thiol fluorescent dyes of formula (I), (II) or (III) are dyes capable of absorbing at an λ abs of between 420 nm and 550 nm and of reemitting in the visible at an λ em of between 550. and 620 nm.
Les composés fluorescents de l'invention contiennent une fonction SY qui peut se trouver sous la forme covalente -S-Y ou ionique -S" Y+ selon la nature de Y et du pH du milieu. Un mode particulier concerne les colorants fluorescents thiols de formule (I) à fonction SY où Y représente un métal alcalin.The fluorescent compounds of the invention contain a SY function which may be in the covalent -SY or ionic -S " Y + form, depending on the nature of Y and the pH of the medium.A particular embodiment relates to the thiol fluorescent dyes of formula ( I) with SY function where Y represents an alkali metal.
Conformément à un autre mode de réalisation particulier de l'invention, dans la formule (I) précitée, Y est un groupement protecteur connu par l'homme du métier comme par exemple ceux décris dans les ouvrages « Protective Groups in Organic Synthesis », T. W. Greene, John Willey & Sons éd., NY, 1981 , pp.193-217 ;According to another particular embodiment of the invention, in formula (I) above, Y is a protective group known to those skilled in the art such as those described in the books "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217;
« Protecting Groups », P. Kocienski, Thieme, 3èmΘ éd., 2005, chap. 5."Protecting Groups", P. Kocienski, Thieme, 3 èmΘ ed., 2005, c. 5.
Particulièrement lorsque Y représente un groupement protecteur de la fonction thiol, Y est choisi parmi les radicaux suivants :Especially when Y represents a protective group of the thiol function, Y is chosen from the following radicals:
• (Ci-C4)alkylcarbonyle ; • (CrOOalkylthiocarbonyle ;(C 1 -C 4 ) alkylcarbonyl; (CrOOalkylthiocarbonyl;
• (Ci-C4)alcoxycarbonyle ;• (Ci-C 4) alkoxycarbonyl;
• (CrCXOalcoxythiocarbonyle ;• (CrCXOalkoxythiocarbonyl;
• (Ci-C4)alkylthio-thiocarbonyle ;• (Ci-C 4) alkylthio-thiocarbonyl;
• (di) (C1-C4) (alkyl)aminocarbonyle ; • (di) (CrC4) (alkyl)aminothiocarbonyle ;• (di) (C 1 -C 4 ) (alkyl) aminocarbonyl; (Di) (CrC 4 ) (alkyl) aminothiocarbonyl;
• arylcarbonyle comme phénylcarbonyle ;Arylcarbonyl as phenylcarbonyl;
• aryloxycarbonyle ;Aryloxycarbonyl;
• aryl(CrC4)alcoxycarbonyle ; • (di) (CrC4) (alkyl)aminocarbonyle comme diméthylaminocarbonyle ;• aryl (CrC 4 ) alkoxycarbonyl; (Di) (CrC 4 ) (alkyl) aminocarbonyl as dimethylaminocarbonyl;
• (Ci-C4)(alkyl)arylaminocarbonyle ;• (Ci-C 4) (alkyl) arylaminocarbonyl;
• carboxy ;• carboxy;
• SO3 " ; M+ avec M+ représentant un métal alcalin tel que le sodium ou le potassium ou alors M+ et M' de la formule (I) sont absents ;• SO 3 " M + with M + representing an alkali metal such as sodium or potassium or M + and M 'of the formula (I) are absent;
• aryle éventuellement substitué tel que le phényle, dibenzosubéryle, ou 1,3,5- cycloheptatriényle,Optionally substituted aryl such as phenyl, dibenzosuberyl, or 1,3,5-cycloheptatrienyl,
• hétéroaryle éventuellement substitué ; dont notamment l'hétéroaryle cationiques ou non, comprenant de 1 à 4 hétéroatomes suivants : i) monocycliques à 5, 6 ou 7 chaînons tels que furanyle ou furyle, pyrrolyle ou pyrryle, thiophényle ou thiényle, pyrazolyle, oxazolyle, oxazolium, isoxazolyle, isoxazolium, thiazolyle, thiazolium, isothiazolyle, isothiazolium, 1 ,2,4-triazolyle, 1 ,2,4-triazolium, 1 ,2,3-triazolyle, 1,2,3- triazolium, 1 ,2,4-oxazolyle, 1 ,2,4-oxazolium, 1 ,2,4-thiadiazolyle, 1 ,2,4- thiadiazolium, pyrylium, thiopyridyle, pyridinium, pyrimidinyle, pyrimidinium, pyrazinyle, pyrazinium, pyridazinyle, pyridazinium, triazinyle, triazinium, tétrazinyle, tétrazinium, azépine, azépinium, oxazépinyle, oxazépinium, thiépinyle, thiépinium, imidazolyle, imidazolium ; ii) bicycliques à 8 à 11 chaînons tels que indolyle, indolinium, benzoimidazolyle, benzoimidazolium, benzoxazolyle, benzoxazolium, dihydrobenzoxazolinyle, benzothiazolyle, benzothiazolium, pyridoimidazolyle, pyridoimidazolium, thiénocycloheptadiényle, ces groupes mono ou bicycliques étant éventuellement substitués par un ou plusieurs groupements tels que (CrC4)alkyle comme méthyle, ou polyhalogéno(CrC4)alkyle comme trifluorométhyle ; iii) ou tricyclique ABC suivant :Optionally substituted heteroaryl; including in particular cationic or non-cationic heteroaryl, comprising from 1 to 4 following heteroatoms: i) monocyclic with 5, 6 or 7 members such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl, isoxazolium thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl, 1 , 2,4-oxazolium, 1,2,4-thiadiazolyl, 1,2,4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium, pyridazinyl, pyridazinium, triazinyl, triazinium, tetrazinyl, tetrazinium, azepine azepinium, oxazepinyl, oxazepinium, thiepinyl, thiepinium, imidazolyl, imidazolium; ii) 8 to 11-membered bicyclic compounds such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazolium, thienocycloheptadienyl, these mono or bicyclic groups being optionally substituted by one or more groups such as CrC 4 ) alkyl as methyl, or polyhalo (C 1 -C 4 ) alkyl as trifluoromethyl; iii) or tricyclic ABC following:
Figure imgf000013_0001
dans lequel les deux cycles A, C comportent éventuellement un hétéroatome, et le cycle B est un cycle à 5, 6 ou 7 chaînons particulièrement à 6 chaînons et contient au moins un hétéroatome comme pypéridyle, pyranyle ; hétérocycloalkyle éventuellement substitué, éventuellement cationique, le groupe hétérocycloalkyle représente notamment un groupe monocyclique saturé ou partiellement saturé à 5, 6 ou 7 chaînons comprenant de 1 à 4 hétéroatomes choisis parmi l'oxygène, le soufre et l'azote, tel que di/tétrahydrofuranyle, di/tétrahydrothiophényle, di/tétrahydropyrrolyle, di/tétrahydropyranyle, di/tétra/hexahydrothiopyranyle, dihydropyridyle, pipérazinyle, pipéridinyle, tétraméthylpipéridinyle, morpholinyle, di/tétra/hexahydroazépinyle, di/tétrahydropyrimidinyle ces groupes étant éventuellement substitués par un ou plusieurs groupes comme (C1-C4) alkyle, oxo ou thioxo ; ou l'hétérocycle représente le groupement suivant :
Figure imgf000013_0001
wherein the two rings A, C optionally comprise a heteroatom, and the ring B is a 5-, 6- or 7-membered particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl; optionally substituted heterocycloalkyl, optionally cationic, the heterocycloalkyl group represents in particular a saturated or partially saturated monocyclic group with 5, 6 or 7 members comprising 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl; , di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydroazepinyl, di / tetrahydropyrimidinyl these groups being optionally substituted with one or more groups such as C 1 -C 4 ) alkyl, oxo or thioxo; or the heterocycle represents the following group:
Figure imgf000014_0001
dans lequel R'c, R'd, R'Θ, R'f, R'9 et R'h, identiques ou différents représentent un atome d'hydrogène ou un groupement (Ci-C4) alkyle, ou alors deux groupement R'9 avec R'h, et/ou R'Θ avec R'f forment un groupement oxo ou thioxo, ou alors R'9 avec R'Θ forment ensemble un cycloalkyle ; et v représente un entier compris inclusivement entre 1 et 3 ; préférentiellement R'c à R'h représentent un atome d'hydrogène ; et An" représente un contre-ion ;
Figure imgf000014_0001
wherein R 'c, R' d, R 'Θ, R' f, R '9 and R' h, identical or different, represent a hydrogen atom or a (Ci-C 4) alkyl, or else two groups R ' 9 with R' h , and / or R ' Θ with R' f form an oxo or thioxo group, or else R ' 9 with R' Θ together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3; preferentially R ' c to R' h represent a hydrogen atom; and An " represents a counterion;
• isothiouronium -C(NR'cR'd)=N+R'ΘR'f; An" avec R'c, R'd, R'Θ et R'f, identiques ou différents représentent un atome d'hydrogène ou un groupement (d-C4)alkyle ; préférentiellement R'c à R'f représentent un atome d'hydrogène ; et An" représente un contre-ion ;• isothiouronium -C (NR ' c R' d ) = N + R ' Θ R'f; An "with R 'c, R' d, R and R' f, like or different, represent a hydrogen atom or a (dC 4) alkyl; preferably, R 'c to R' f represent a hydrogen atom, hydrogen, and An " represents a counterion;
• isothiourée -C(NR'cR'd)=NR'Θ; avec R'c, R'd et R'Θ tels que définis précédemment ;• isothiourea -C (NR ' c R' d ) = NR 'Θ; with R ' c , R' d and R ' Θ as defined above;
• (di)aryl(CrC4)alkyle éventuellement substitué tel que le 9-anthracénylméthyle, phénylméthyle ou diphénylméthyle éventuellement substitué par un plusieurs groupements notamment choisis parmi (C1-C4) alkyle, (Ci-C4) alcoxy comme le méthoxy, hydroxy, (CrC4) alkylcarbonyle, (di) (CrC4) (alkyl)amino comme le diméthylamino ;Optionally substituted (di) aryl (C r C 4 ) alkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted with one or more groups chosen in particular from (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, for example methoxy, hydroxy, (C 1 -C 4 ) alkylcarbonyl, (di) (C 1 -C 4 ) (alkyl) amino such as dimethylamino;
• (di)hétéroaryl(CrC4)akyle éventuellement substitué, le groupe hétéroaryle est notamment, cationique ou non, monocyclique, comprenant 5 ou 6 chaînons et de 1 à 4 hétéroatomes choisis parmi l'azote, l'oxygène et le soufre, tels que les groupes pyrrolyle, furanyle, thiophényle, pyridyle, pyridyle N-oxyde tels que le 4-pyridyle ou 2-pyridyl-N-oxyde, pyrylium, pyridinium, triazinyle, éventuellement substitué par un ou plusieurs groupement tel que alkyle particulièrement méthyle, avantageusement le (di)hétéroaryl(CrC4)akyle est (di)hétéroaryl- méthyle ou (di)hétéroaryléthyle ;(Di) heteroaryl (C r C 4 ) optionally substituted alkyl, the heteroaryl group is in particular, cationic or otherwise, monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide groups such as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium, triazinyl, optionally substituted by one or more groups such as alkyl particularly methyl, advantageously (di) heteroaryl (CrC 4 ) alkyl is (di) heteroaryl methyl or (di) heteroarylethyl;
• CR1R2R3 avec R1, R2 et R3 identiques ou différents, représentant un atome d'halogène ou un groupe choisi parmi : - (C1-C4) alkyle ;• CR 1 R 2 R 3 with R 1 , R 2 and R 3, which may be identical or different, representing a halogen atom or a group chosen from: - (C 1 -C 4 ) alkyl;
- (C1-C4) alcoxy ;- (C 1 -C 4 ) alkoxy;
- aryle éventuellement substitué tel que phényle éventuellement substitué par un ou plusieurs groupements comme (CrC4)alkyle, (CrC4)alcoxy, hydroxy ; - hétéroaryle éventuellement substitué tel que thiophényle, furanyle, pyrrolyle, pyranyle, pyridyle, éventuellement substitué par un groupement (Ci-C4)alkyle ;optionally substituted aryl such as phenyl optionally substituted by one or more groups such as (CrC 4 ) alkyl, (CrC 4 ) alkoxy, hydroxy; optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl or pyridyl, optionally substituted with a (C 1 -C 4 ) alkyl group;
- P(Z1 )R' 1R12R'3 avec R'1, et R'2 identiques ou différents représentent un groupement hydroxy, (C1-C4JaIcOXy ou alkyle, R'3 représente un groupement hydroxy ou (CrC4)alcoxy, et Z1 représente un atome d'oxygène ou de soufre ;- P (Z 1 ) R ' 1 R 12 R' 3 with R ' 1 , and R' 2 identical or different represent a hydroxyl group, (C 1 -C 4 ) alkyl or alkyl, R ' 3 represents a hydroxyl group or C r C 4 ) alkoxy, and Z 1 represents an oxygen or sulfur atom;
• cyclique stériquement encombré tel que le groupe adamantyle ; etSterically hindered cyclic such as the adamantyl group; and
• alcoxy(CrC4)alkyle éventuellement substitué tels que le méthoxy méthyle (MOM), éthoxyéthyle (EOM) et l'isobutoxyméthyle.Optionally substituted alkoxy (CrC 4 ) alkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.
Selon un mode de réalisation particulier les colorants fluorescents thiols protégés de formule (I) comportent un groupement Y i) hétéroaryle monocyclique à 5 ou 6 chaînons aromatiques, cationiques comprenant de 1 à 4 hétéroatomes choisis parmi l'oxygène, le soufre et l'azote, tels que oxazolium, , isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1 ,2,3-triazolium, 1 ,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyle, pyrazinium, pyridazinium, triazinium, tétrazinium, oxazépinium, thiépinyle, thiépinium, imidazolium ; ii) hétéroaryle bicyclique à 8 à 11 chaînons cationique tels que indolinium, benzoimidazolium, benzoxazolium, benzothiazolium, ces groupes hétéroaryle mono ou bicycliques étant éventuellement substitués par un ou plusieurs groupements tels que alkyle comme méthyle, ou polyhalogéno(Ci-C4)alkyle ∞mme trifluorométhyle ; iii) ou hétérocyclique suivant :According to a particular embodiment, the protected thiol fluorescent dyes of formula (I) contain a cationic aromatic 5- or 6-membered monocyclic heterocyclic group, Y, comprising 1 to 4 heteroatoms chosen 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, tetrazinium, oxazepinium, thiepinyl, thiepinium, imidazolium; ii) cationic 8 to 11-membered bicyclic heteroaryl such as indolinium, benzoimidazolium, benzoxazolium, benzothiazolium, these mono or bicyclic heteroaryl groups optionally being substituted by one or more groups such as alkyl like methyl, or polyhalo (Ci-C 4) alkyl ∞mme trifluoromethyl; iii) or heterocyclic according to:
Figure imgf000016_0001
dans lequel R'c et R'd, identiques ou différents, représentent un atome d'hydrogène ou un groupement (d-C4)alkyle ; préférentiellement R'c à R'd représentent un groupement
Figure imgf000016_0001
wherein R ' c and R' d , identical or different, represent a hydrogen atom or a group (dC 4 ) alkyl; preferentially R ' c to R' d represent a grouping
(d-C4)alkyle tel que méthyle ; et An" représente un contre-ion.(dC 4 ) alkyl such as methyl; and An " represents a counterion.
Particulièrement Y représente un groupement choisi parmi 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, triazinium et imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, ces groupements étant éventuellement substitués par un ou plusieurs groupes (CrC4) alkyle notamment méthyle.Especially Y represents a group chosen 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, triazinium and imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted by one or more (CrC 4 ) alkyl groups including methyl.
En particulier Y représente un métal alcalin ou un groupement protecteur tel que: > (CrC4)alkylcarbonyle comme méthylcarbonyle ou éthylcarbonyle ;In particular Y represents an alkali metal or a protective group such as:> (C r C 4 ) alkylcarbonyl such as methylcarbonyl or ethylcarbonyl;
> arylcarbonyle comme phénylcarbonyle ;arylcarbonyl, such as phenylcarbonyl;
> (CrC4)alcoxycarbonyle ;(C r C 4 ) alkoxycarbonyl;
> aryloxycarbonyle ;> aryloxycarbonyl;
> aryl(CrC4)alcoxycarbonyle ; > (di) (CrC4) (alkyl)aminocarbonyle comme diméthylaminocarbonyle;> aryl (C 1 -C 4 ) alkoxycarbonyl; (di) (CrC 4 ) (alkyl) aminocarbonyl as dimethylaminocarbonyl;
> (CrC4)(alkyl)arylaminocarbonyle ;(C r C 4 ) (alkyl) arylaminocarbonyl;
> aryle éventuellement substitué tel que le phényle ;optionally substituted aryl such as phenyl;
> hétéroaryle monocyclique à 5 ou 6 chaînons tels que imidazolyle ou pyridyle ;monocyclic 5- or 6-membered heteroaryl such as imidazolyl or pyridyl;
> hétéroaryle monocyclique cationique à 5, 6 chaînons tels que pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium ; ces groupements étant éventuellement substitué par un ou plusieurs, identiques ou différents, groupes (CrC4)alkyle tel que méthyle;Cationic monocyclic 5- to 6-membered heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted with one or more, identical or different, (CrC 4 ) alkyl groups such as methyl;
> hétéroaryle bicyclique cationique à 8 à 11 chaînons tels que benzoimidazolium, ou le benzoxazolium ; ces groupements étant éventuellement substitué par un ou plusieurs, identiques ou différents, groupes (CrC4)alkyle tel que méthyle ; > hétérocycle cationique de formule suivante :8 to 11-membered cationic bicyclic heteroaryl such as benzoimidazolium, or benzoxazolium; these groups being optionally substituted by one or more, identical or different, (C 1 -C 4 ) alkyl groups such as methyl; cationic heterocycle of following formula:
Figure imgf000017_0001
Figure imgf000017_0001
> isothiouronium -C(NH2)=N+H2; An";> isothiouronium -C (NH 2 ) = N + H 2 ; An " ;
> isothiourée -C(NH2)=NH ;> isothiourea -C (NH 2 ) = NH;
> SO3 " , M+ avec M+ représentant un métal alcalin tel que le sodium ou le potassium ou alors M+ et M' de la formule (I) sont absents.> SO 3 " , M + with M + representing an alkali metal such as sodium or potassium or M + and M 'of the formula (I) are absent.
A titre d'exemple de colorants fluorescents de formule (I), (II), ou (III), on peut citer notamment les composés suivants :By way of example of fluorescent dyes of formula (I), (II) or (III), mention may be made in particular of the following compounds:
Figure imgf000017_0002
Figure imgf000017_0002
[I] [H][I] [H]
Figure imgf000017_0003
Figure imgf000017_0003
2An" 6
Figure imgf000018_0001
8
2An " 6
Figure imgf000018_0001
8
Avec An" représentant un ∞ntre-ion anionique.With An " representing anionic ionion.
Les colorants thiols protégés de formule (I1) et (I") peuvent être synthétisés en deux étapes. La première étape consistant à préparer le colorant thiol non protégé (II) selon les méthodes connues de l'homme de l'art comme par exemple « Thiols and organic Sulfides », « Thiocyanates and Isothiocyanates, organic », Ullmann's Encyclopedia, Wiley-VCH, Weinheim, 2005. Et la deuxième étape consistant à protéger la fonction thiol selon les méthodes classiques connues par l'homme du métier pour conduire aux colorants thiols protégés de formule (I1) et (I"). A titre d'exemple pour protéger la fonction thiol -SH du colorant thiol on peut utiliser les méthodes des ouvrages « Protective Groups in Organic Synthesis », T. W. Greene, John Willey & Sons éd., NY, 1981, pp.193-217 ; « Protecting Groups », P. Kocienski, Thieme, 3èmΘ éd., 2005, chap. 5.The protected thiol dyes of formula (I 1 ) and (I ") can be synthesized in two steps: the first step of preparing the unprotected thiol dye (II) according to methods known to those skilled in the art as per For example 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 to those skilled in the art for driving. protected thiol dyes of formula (I 1 ) and (I "). By way of example, to protect the thiol -SH function of the thiol dye, the methods of the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217; "Protecting Groups", P. Kocienski, Thieme, 3 èmΘ ed., 2005, c. 5.
Nous pouvons illustrer cette méthode par la méthode consistant i) à générer le colorant fluorescent thiol de formule (II) par réduction d'un colorant fluorescent à deux chromophores portant une fonction disulfure -S-S- tels que (III) et ii) à protéger selon les méthodes classiques ladite fonction thiol de (II) avec le réactif 7 Y'R pour accéder aux colorants fluorescents thiols protégés de formule (I1). Le composé thiol (II) peut également être métallé avec un métal alcalin ou alcalino terreux Met* pour conduire au colorant fluorescent thiolate de formule (I").We can illustrate this method by the method consisting of i) generating the thiol fluorescent dye of formula (II) by reducing a fluorescent dye to two chromophores bearing a disulfide function -SS- such that (III) and ii) to be protected according to conventional methods said thiol function of (II) with the reagent 7 Y'R to access thiol protected fluorescent dyes of formula (I 1 ). The thiol compound (II) may also be metallized with an alkali metal or alkaline earth metal Met * to yield the thiolate fluorescent dye of formula (I ").
Figure imgf000018_0002
avec Y' représentant un groupement protecteur de fonction thiol ; Met* représentant un métal alcalin ou un métal alcalino terreux, particulièrement le sodium ou le potassium ; et Gp" représentant un contre-ion anionique consécutif au départ du groupe partant. Les contre-ions Gp" des composés (Mi), (M), (I1) et (I") ci-dessus peuvent être remplacés par des contre-ions An' d'autres natures à partir de méthodes connues par l'homme du métier notamment par résine échangeuse d'ion.
Figure imgf000018_0002
with Y 'representing a protecting group of thiol function; Met * representing an alkali metal or an alkaline earth metal, particularly sodium or potassium; and Gp " representing an anionic counter-ion subsequent to leaving the leaving group The counterions Gp " of the compounds (Mi), (M), (I 1 ) and (I ") above can be replaced by counter-ions -ions An 'other natures from methods known to those skilled in the art in particular by ion exchange resin.
On pourra également utiliser un réactif thiol (α) Y'-SH comprenant un groupement Y' tel que défini précédemment dont la fonction nucléophile SH peut réagir sur l'atome de carbone en alpha de l'atome d'halogène porté par le chromophore fluorescent 7 pour conduire au colorant fluorescent thiol protégé de formule (I1):It is also possible to use a thiol reagent (α) Y'-SH comprising a group Y 'as defined previously, whose nucleophilic function SH can react on the carbon atom alpha of the halogen atom borne by the fluorescent chromophore 7 to yield the protected thiol fluorescent dye of formula (I 1 ):
Figure imgf000019_0001
Figure imgf000019_0001
(Z) avec HaI représentant un atome d'halogène nucléofuge tel que le brome, l'iode ou le chlore. Plus particulièrement on pourra substituer un groupement partant nucléofuge par un groupement thiourée (S=C(NRR)NRR) pour générer les isothiouroniums. Par exemple si le groupement thiourée est une thioimidazolinium (β), le schéma réactionnel est le suivant :(Z) with HaI representing a nucleofugal halogen atom such as bromine, iodine or chlorine. More particularly, it will be possible to substitute a nucleofugal leaving group with a thiourea group (S = C (NRR) NRR) to generate the isothiouroniums. For example, if the thiourea group is a thioimidazolinium (β), the reaction scheme is as follows:
Figure imgf000019_0002
avec R'c, R'd, HaI, An" et Gp" sont tels que définis précédemment.
Figure imgf000019_0002
with R ' c , R' d , HaI, An " and Gp " are as defined above.
Une variante est d'utiliser à la place de l'halogénure comprenant le chromophore fluorescent (a) un chromophore comprenant un autre type de nucléofuge tel que le tosylate, mésylate ou le triflate.An alternative is to use in place of the halide comprising the fluorescent chromophore (a) a chromophore comprising another type of nucleofuge such as tosylate, mesylate or triflate.
Selon une autre variante il est possible de générer un intermédiaire imidazoline à partir de l'halogénure comprenant le chromophore fluorescent (a1) et une thioimidazoline (b1) pour conduire après alkylation par un réactif R-Gp' avec R représentant un groupement alkyle et Gp' un groupe partant tel qu'un halogène comme le chlore, brome, iode, ou un groupement mésylate ou tosylate, au colorant fluorescent de formule (I"").According to another variant it is possible to generate an imidazoline intermediate from the halide comprising the fluorescent chromophore (a 1 ) and a thioimidazoline (b 1 ) to conduct after alkylation with a reagent R-Gp 'with R representing an alkyl group and Gp 'a leaving group such as a halogen like chlorine, bromine, iodine, or a mesylate or tosylate group with a fluorescent dye of formula (I "").
Figure imgf000020_0001
Figure imgf000020_0001
MM
Alkylation (R'd-GP')Alkylation (R'd-GP ')
Figure imgf000020_0002
Figure imgf000020_0002
Selon un autre procédé, les colorants fluorescents thiols protégés peuvent être générés à partir de composé (b) et du réactif thiol comprenant un groupe partant Gp tel que (ç). A titre d'exemple le groupe partant peut être un mésylate, tosylate, triflate ou halogénure:In another method, the protected thiol fluorescent dyes can be generated from the compound (b) and the thiol reagent comprising a leaving group Gp such that (c). By way of example, the leaving group may be a mesylate, tosylate, triflate or halide:
Figure imgf000020_0003
Figure imgf000020_0003
MM
Conformément à une autre possibilité, les colorants fluorescents thiols protégés de formule (I) selon l'invention peuvent être obtenus par condensation d'un dérivé deAccording to another possibility, the protected thiol fluorescent dyes of formula (I) according to the invention can be obtained by condensation of a derivative of
4-diméthylamino benzaldéhyde avec un réactif contenant un « méthylène activé » tel que le dérivé 4-méthylpyridinium (d) comprenant également la fonction thiol. Cette réaction est communément appelée condensation de « Knoevenagel ».4-dimethylamino benzaldehyde with a reagent containing "activated methylene" such as the 4-methylpyridinium derivative (d) also comprising the thiol function. This reaction is commonly known as "Knoevenagel" condensation.
Figure imgf000020_0004
Figure imgf000020_0004
avec Y et An" tels que définis précédemment et G représentant un atome d'oxygène, de soufre, ou un groupement NRa avec Ra représentant un atome d'hydrogène ou un groupement alkyle. On pourra se référer à l'ouvrage Advanced Organic Chemistry, « Reactions, Mechanisms and Structures », J. March, 4èmΘ Ed, John Willey & Sons, 1992 ou T. W. Greene « Protective Groups in Organic Synthesis », pour avoir plus de détails sur les conditions opératoires mises en œuvre pour les procédés mentionnés ci-dessus. Les colorants fluorescents thiols formés peuvent être transformés en colorants fluorescents thiols protégés -S Y' par la protection du thiol -SH en utilisant les groupements protecteurs classiques. Les colorants fluorescents thiols sont métallés en utilisant également les méthodes classiques connues par l'homme du métier telles que celles décrites dans Advanced Organic Chemistry, « Reactions, Mechanisms and Structures », J. March, 4èmΘ Ed, John Willey & Sons, NY, 1992.with Y and An " as defined above and G representing an oxygen atom, sulfur, or a group NR a with R a representing a hydrogen atom or an alkyl group. Reference may be made to the book Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4 èmΘ Ed, John Wiley & Sons, 1992, or TW Greene "Protective Groups in Organic Synthesis" for more details on the operating conditions used for the processes mentioned above. The thiol fluorescent dyes formed can be converted to protected thiol stain -SY 'by protecting the thiol -SH using conventional 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 èmΘ Ed, John Wiley & Sons, NY , 1992.
Les colorants thiols protégés peuvent êtres déprotégés par voies classiques telles que celles décrites dans les ouvrages « Protective Groups in Organic Synthesis », T. W. Greene, John Willey & Sons éd., NY, 1981 ; « Protecting Groups », P. Kocienski, Thieme, 3èmΘ éd., 2005. Les réactifs de départs sont commerciaux ou accessibles par les méthodes classiques connues par l'homme du métier. A titre d'exemple il est possible de synthétiser le réactif (Ml) à partir de 2 équivalents de 4-méthylpyridine 1 et un équivalent de réactif disulfure comprenant deux groupe partant Gp, pour conduire au sel de dipyridinium disulfure 3 qui peut se condenser à son tour avec deux équivalents de 4 pour conduire à (Ml).Protected thiol dyes may be deprotected by conventional routes such as those described in the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005. The starting reagents are commercial or accessible by conventional methods known to those skilled in the art. By way of example, it is possible to synthesize the reagent (M1) from 2 equivalents of 4-methylpyridine 1 and one equivalent of disulfide reagent comprising two leaving group Gp, to yield the dipyridinium disulfide salt 3 which can condense on turn with two equivalents of 4 to lead to (Ml).
Figure imgf000021_0001
avec Gp représentant un groupe partant nucléofuge, comme par exemple mésylate, tosylate, triflate ou halogénure.
Figure imgf000021_0001
with Gp representing a leaving group nucleofuge, such as mesylate, tosylate, triflate or halide.
La composition de l'invention contient au moins un colorant fluorescent thiol de formule (I). Outre la présence d'au moins un colorant fluorescent de formule (I), (II) ou (III), la composition de l'invention peut également contenir un agent réducteur. Cet agent réducteur peut être choisi parmi les thiols par exemple la cystéine, l'homocystéine, l'acide thiolactique, les sels de ces thiols, les phosphines, le bisulfite, les sulfites, l'acide thioglycolique, ainsi que ses esters, notamment le monothioglycolate de glycérol, et le thioglycérol. Cet agent réducteur peut aussi être choisi parmi les borohydrures et leurs dérivés, comme par exemple les sels du borohydrure, du cyanoborohydrure, du triacétoxyborohydrure, du triméthoxyborohydrure : sels de sodium, lithium, potassium, calcium, ammoniums quaternaires (tétraméthylammonium, tétraéthylammonium, tétra n-butylammonium, benzyltriéthylammonium); le catéchol-borane.The composition of the invention contains at least one thiol fluorescent dye of formula (I). In addition to 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, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, for example the salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra n-butylammonium, benzyltriethylammonium); catechol borane.
La composition tinctoriale utile dans l'invention contient en général une quantité de colorant fluorescent de formule (I), (II) ou (III) comprise entre 0,001 et 50% par rapport au poids total de la composition. De préférence, cette quantité est comprise entre 0,005 et 20% en poids et encore plus préférentiellement entre 0,01 et 5% en poids par rapport au poids total de la composition.The dye composition useful in the invention generally contains a quantity of fluorescent dye of formula (I), (II) or (III) of between 0.001 and 50% relative to 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.
La composition tinctoriale peut en outre contenir des colorants directs additionnels. Ces colorants directs sont par exemple choisis parmi les colorants directs nitrés benzéniques neutres, acides ou cationiques, les colorants directs azoïques neutres, acides ou cationiques, les colorants tétraazapentaméthiniques, les colorants quinoniques et en particulier anthraquinoniques neutres, acides ou cationiques, les colorants directs aziniques, les colorants directs triarylméthaniques, les colorants directs indoaminiques et les colorants directs naturels.The dye composition may further contain additional direct dyes. These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
Parmi les colorants directs naturels, on peut citer la lawsone, la juglone, l'alizarine, la purpurine, l'acide carminique, l'acide kermésique, la purpurogalline, le protocatéchaldéhyde, l'indigo, l'isatine, la curcumine, la spinulosine, l'apigénidine. On peut également utiliser les extraits ou décoctions contenant ces colorants naturels et notamment les cataplasmes ou extraits à base de henné.Among the natural direct dyes that may be mentioned are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.
La composition tinctoriale peut contenir une ou plusieurs base d'oxydation et/ou un ou plusieurs coupleurs conventionnellement utilisés pour la teinture de fibres kératiniques.The dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers.
Parmi les bases d'oxydation, on peut citer les para-phénylènediamines, les bis- phénylalkylènediamines, les para-aminophénols, les bis-para-aminophénols, les ortho- aminophénols, les bases hétérocycliques et leurs sels d'additionAmong the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.
Parmi ces coupleurs, on peut notamment citer les méta- phénylènediamines, les méta-aminophénols, les méta-diphénols, les coupleurs naphtaléniques, les coupleurs hétérocycliques et leur sels d'addition. Le ou les coupleurs sont chacun généralement présents en quantité comprise entre 0,001 et 10 % en poids du poids total de la composition tinctoriale, de préférence entre 0,005 et 6 %.Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.
La ou les bases d'oxydation présentes dans la composition tinctoriale sont en général présentes chacune en quantité comprise entre 0,001 à 10 % en poids du poids total de la composition tinctoriale, de préférence entre 0,005 et 6 % en poids.The oxidation base (s) present in the dyeing composition are generally present each in an amount of between 0.001% and 10% by weight of the weight. total of the dyeing composition, preferably between 0.005 and 6% by weight.
D'une manière générale, les sels d'addition des bases d'oxydation et des coupleurs utilisables dans le cadre de l'invention sont notamment choisis parmi les sels d'addition avec un acide tels que les chlorhydrates, les bromhydrates, les sulfates, les citrates, les succinates, les tartrates, les lactates, les tosylates, les benzènesulfonates, les phosphates et les acétates et les sels d'addition avec une base telles que les hydroxydes de métal alcalin comme la soude, la potasse, l'ammoniaque, les aminés ou les alcanolamines.In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
Le milieu approprié pour la teinture, appelé aussi support de teinture, est un milieu cosmétique généralement constitué par de l'eau ou par un mélange d'eau et d'au moins un solvant organique. A titre de solvant organique, on peut par exemple citer les alcanols inférieurs en d-C4, tels que l'éthanol et l'isopropanol ; les polyols et éthers de polyols comme le 2-butoxyéthanol, le propylèneglycol, le monométhyléther de propylèneglycol, le monoéthyléther et le monométhyléther du diéthylèneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, et leurs mélanges.The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent. As organic solvent, there may be mentioned, for example lower alkanols dC 4 , such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
Les solvants lorsqu'ils sont présents sont, de préférence présents dans des proportions de préférence comprises entre 1 et 40 % en poids environ par rapport au poids total de la composition tinctoriale, et encore plus préférentiellement entre 5 et 30 % en poids environ.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 approximately.
Selon une variante, l'invention contient un agent réducteur capable de réduire les liaisons disulfures de la kératine. Cet agent réducteur est tel que défini précédemment.According to one variant, the invention contains a reducing agent capable of reducing the disulfide bonds of keratin. This reducing agent is as defined above.
La composition tinctoriale peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux, tels que des agents tensioactifs anioniques, cationiques, non ioniques, amphotères, zwittérioniques ou leurs mélanges, des polymères anioniques, cationiques, non ioniques, amphotères, zwittérioniques ou leurs mélanges, des agents épaississants minéraux ou organiques, et en particulier les épaississants associatifs polymères anioniques, cationiques, non ioniques et amphotères, des agents antioxydants, des agents de pénétration, des agents séquestrants, des parfums, des tampons, des agents dispersants, des agents de conditionnement tels que par exemple des silicones volatiles ou non volatiles, modifiées ou non tels que les silicones aminés, des agents filmogènes, des céramides, des agents conservateurs, des agents opacifiants, des polymères conducteurs.The dye composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers. or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, film-forming agents, ceramides, preserving agents, opacifying agents, conductive polymers.
Les adjuvants ci dessus sont en général présents en quantité comprise pour chacun d'eux entre 0,01 et 20 % en poids par rapport au poids de la composition.The adjuvants above are generally present in an amount each of them between 0.01 and 20% by weight relative to the weight of the composition.
Bien entendu, l'homme de l'art veillera à choisir ce ou ces éventuels composés complémentaires de manière telle que les propriétés avantageuses attachées intrinsèquement à la composition de teinture conforme à l'invention ne soient pas, ou substantiellement pas, altérées par la ou les adjonctions envisagées.Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, impaired by the or the additions envisaged.
Le pH de la composition tinctoriale est généralement compris entre 3 et 14 environ, et de préférence entre 5 et 11 environ. Il peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques ou bien encore à l'aide de systèmes tampons classiques. Parmi les agents acidifiants, on peut citer, à titre d'exemple, les acides minéraux ou organiques comme l'acide chlorhydrique, l'acide orthophosphorique, l'acide sulfurique, les acides carboxyliques comme l'acide acétique, l'acide tartrique, l'acide citrique, l'acide lactique, les acides sulfoniques.The pH of the dyeing composition is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.
Parmi les agents alcalinisants on peut citer, à titre d'exemple, l'ammoniaque, les carbonates alcalins, les alcanolamines telles que les mono-, di- et triéthanolamines ainsi que leurs dérivés, les hydroxydes de sodium ou de potassium et les composés de formule (γ) suivante : aj / a2Among the alkalinizing agents that may be mentioned, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (γ): aj / a2
N W8-NNW 8 -N
R34 Ra3 (γ) dans laquelle Wa est un reste propylène éventuellement substitué par un groupement hydroxy ou un radical alkyle en Ci-C4 ; Rai, Ra2, Ra3 et Ra4, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en CrC4 ou hydroxyalkyle en C1-C4.R 3 4 R a3 (γ) wherein W is a propylene residue optionally substituted with a hydroxy group or an alkyl radical Ci-C 4; R i, R a2, R a3 and R a4, identical or different, represent a hydrogen atom, an alkyl radical in C r -C 4 hydroxyalkyl or C 1 -C 4.
La composition tinctoriale peut se présenter sous des formes diverses, telles que sous forme de liquide, de crème, de gel, ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux.The dye composition may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratinous fibers, and in particular hair.
Selon un mode de réalisation particulier dans le procédé de l'invention un agent réducteur peut être appliqué en pré-traitement avant l'application de la composition contenant au moins un colorant fluorescent de formule (I) ou (II).According to a particular embodiment in the method of the invention, a reducing agent may be applied pre-treatment before the application of the composition containing at least one fluorescent dye of formula (I) or (II).
Cet agent réducteur peut être choisi parmi les thiols par exemple la cystéine, l'homocystéine, l'acide thiolactique, les sels de ces thiols, les phosphines, le bisulfite, les sulfites, l'acide thioglycolique, ainsi que ses esters, notamment le monothioglycolate de glycérol, et le thioglycérol. Cet agent réducteur peut aussi être choisi parmi les borohydrures et leurs dérivés, comme par exemple les sels du borohydrure, du cyanoborohydrure, du triacétoxyborohydrure, du triméthoxyborohydrure : sels de sodium, lithium, potassium, calcium, ammoniums quaternaires (tétraméthylammonium, tétraéthylammonium, tétra n-butylammonium, benzyltriéthylammonium); le catécholborane.This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol. This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane.
Ce prétraitement peut être de courte durée, notamment de 0,1 seconde à 30 minutes, de préférence de 1 minute à 15 minutes avec un agent réducteur tel que cité précédemment.This pretreatment may be of short duration, in particular from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes with a reducing agent as mentioned above.
Selon un autre procédé, la composition comprenant au moins un colorant fluorescent de formule (I), (II) ou au moins un colorant disulfure de formule (III) contient également au moins un agent réducteur tel que défini précédemment. Cette composition est alors appliquée aux cheveux.According to another method, the composition comprising at least one fluorescent dye of formula (I), (II) or at least one disulfide dye of formula (III) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
Le procédé de l'invention peut être précédé d'une étape de déprotection visant à restituer in-situ la fonction SH du colorant de formule (I).The process of the invention may be preceded by a deprotection step intended to restore in situ the SH function of the dye of formula (I).
A titre d'exemple il est possible de déprotéger la fonction S-Y avec Y groupement protecteur en ajustant le pH comme suit :By way of example, it is possible to deprotect the S-Y function with Y protecting group by adjusting the pH as follows:
Figure imgf000025_0001
Figure imgf000025_0001
L'étape de déprotection peut également être réalisée au cour d'une étape de prétraitement des cheveux comme par exemple, le prétraitement réducteur des cheveux. Selon une variante, l'agent réducteur est ajouté à la composition tinctoriale contenant au moins un colorant fluorescent de formule (I), (II) ou au moins un colorant de formule (III) au moment de l'emploi.The deprotection step can also be carried out in the course of a hair pretreatment step such as, for example, the reducing pretreatment of the hair. According to one variant, the reducing agent is added to the dyeing composition containing at least one fluorescent dye of formula (I), (II) or at least one dye of formula (III) at the time of use.
Selon une autre variante, l'agent réducteur est appliqué en post-traitement, après l'application de la composition contenant au moins un colorant fluorescent thiol (I). La durée du post traitement avec l'agent réducteur peut être courte, par exemple de 0,1 seconde à 30 minutes de préférence de 1 minute à 15 minutes, avec un agent réducteur tel que décrit précédemment. Selon un mode de réalisation particulier l'agent réducteur est un agent de type thiol ou borohydrure tel que décrit précédemment. Un mode de réalisation particulier de l'invention concerne un procédé consistant à appliquer directement une composition comprenant au moins un colorant fluorescent de formule (I), (II) ou (III).According to another variant, the reducing agent is applied in post-treatment, after the application of the composition containing at least one thiol fluorescent dye (I). The duration of the post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above. According to a particular embodiment, the reducing agent is a thiol or borohydride type agent as described above. A particular embodiment of the invention relates to a method of directly applying a composition comprising at least one fluorescent dye of formula (I), (II) or (III).
Selon un mode de réalisation particulier, le procédé de coloration avec effet éclaircissant ne nécessite pas de pré ou post-traitement réducteurs, et consiste à appliquer une composition comprenant au moins un colorant fluorescent thiol de formule (I), (II) ou (III) exempt de réducteur.According to one particular embodiment, the lightening-effect dyeing method does not require any pre-or post-treatment reducing agents, and consists in applying a composition comprising at least one thiol fluorescent dye of formula (I), (II) or (III ) free of reducer.
Selon un autre mode de réalisation particulier le procédé de coloration consiste à appliquer sur les matières kératiniques une composition comprenant au moins un colorant disulfure de formule (III) mélangée au préalable à un agent réducteur tel que défini précédemment.According to another particular embodiment, the dyeing process consists in applying to the keratin materials a composition comprising at least one disulfide dye of formula (III) premixed with a reducing agent as defined above.
Une autre variante de l'invention concerne un procédé de coloration consistant à appliquer en un temps sur les matières kératiniques une composition tinctoriale, comprenant dans un milieu cosmétique approprié, au moins un colorant fluorescent disulfure de formule (III) ; et un agent réducteur. Particulièrement la composition tinctoriale comprenant au moins un colorant disulfure de formule (III) et l'agent réducteur sont mélangés ensemble avant l'application sur les matières kératinique juste avant application.Another variant of the invention relates to a dyeing method consisting in applying in a time to the keratin materials a dyeing composition comprising, in a suitable cosmetic medium, at least one disulfide fluorescent dye of formula (III); and a reducing agent. In particular, the dye composition comprising at least one disulfide dye of formula (III) and the reducing agent are mixed together before application to the keratin materials just before application.
Un traitement avec un agent oxydant peut éventuellement être associé. On pourra utiliser n'importe quel type d'agent oxydant classique dans le domaine. Ainsi, il peut être choisi parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bramâtes de métaux alcalins, les persels tels que les perborates et les persulfates, ainsi que les enzymes parmi lesquelles on peut citer les peroxydases, les oxydo-réductases à 2 électrons telles que les uricases et les oxygénases à 4 électrons comme les laccases. L'utilisation du peroxyde d'hydrogène est particulièrement préférée. Cet agent oxydant peut être appliqué sur les fibres avant ou après l'application de la composition contenant au moins un colorant fluorescent thiol de formule (I), (II) ou (III).A treatment with an oxidizing agent may optionally be associated. Any type of conventional oxidizing agent may be used in the art. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, as well as the enzymes among which may be mentioned peroxidases, oxides and the like. 2-electron reductases such as uricases and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred. This oxidizing agent may be applied to the fibers before or after the application of the composition containing at least one thiol fluorescent dye of formula (I), (II) or (III).
L'application de la composition tinctoriale selon l'invention est généralement effectuée à température ambiante. Elle peut cependant être réalisée à des températures variant de 20 à 1800C.The application of the dye composition according to the invention is generally carried out at room temperature. However, it can be carried out at temperatures ranging from 20 to 180 ° C.
L'invention a aussi pour objet un dispositif à plusieurs compartiments ou "kit" de teinture dans lequel un premier compartiment renferme une composition tinctoriale comprenant au moins un colorant fluorescent thiol de formule (I), (II) ou (III) et un deuxième compartiment renferme un agent réducteur capable de réduire les fonctions disulfures des matières kératiniques ou la liaison disulfure du colorant (III).The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains a dye composition comprising at least one thiol fluorescent dye of formula (I), (II) or (III) and a second compartment contains a reducing agent capable of reducing the disulfide functions of the keratin materials or the disulfide bond of the dye (III).
L'un de ces compartiments peut en outre contenir un ou plusieurs autres colorants de type colorant direct ou colorant d'oxydation.One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye.
Elle concerne aussi un dispositif à plusieurs compartiments dans lequel un premier compartiment contient une composition tinctoriale comprenant au moins un colorant fluorescent thiol de formule (I) ou (II) ; un deuxième compartiment contient un agent réducteur capable de réduire la liaison disulfure des matières kératiniques ; un troisième compartiment contient un agent oxydant.It also relates to a multi-compartment device in which a first compartment contains a dye composition comprising at least one fluorescent thiol dye of formula (I) or (II); a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials; a third compartment contains an oxidizing agent.
Alternativement, le dispositif de teinture contient un premier compartiment renfermant une composition tinctoriale qui comprend au moins un colorant fluorescent thiol protégé de formule (I) et un deuxième compartiment renfermant un agent capable de déprotéger le thiol protégé pour libérer le thiol.Alternatively, the dyeing device contains a first compartment containing a dye composition which comprises at least one protected thiol fluorescent dye of formula (I) and a second compartment containing an agent capable of deprotecting the protected thiol to release the thiol.
Chacun des dispositifs mentionnés ci-dessus peut être équipé d'un moyen permettant de délivrer sur les cheveux le mélange souhaité, par exemple tel que les dispositifs décrits dans le brevet FR2 586 913.Each of the devices mentioned above can be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2 586 913.
Les exemples qui suivent servent à illustrer l'invention sans toutefois présenter un caractère limitatif. Les colorants fluorescents thiols des exemples ci-après ont été entièrement caractérisés par les méthodes spectroscopiques et spectrométriques classiques. EXEMPLESThe examples which follow serve to illustrate the invention without, however, being limiting in nature. The thiol fluorescent dyes of the examples below have been fully characterized by conventional spectroscopic and spectrometric methods. EXAMPLES
EXEMPLES DE SYNTHESEEXAMPLES OF SYNTHESIS
Synthèse du dibromure de 1 ,1 '-(disulfanediyldiéthane-2,1-diyl)bis(4-{(E)-2-[4- (diméthylamino)phényl]vinyl}pyridinium) [II]Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4 - {(E) -2- [4- (dimethylamino) phenyl] vinyl} pyridinium dibromide [II]
Figure imgf000028_0001
Figure imgf000028_0001
[H][H]
Schéma de synthèseDiagram of synthesis
Figure imgf000028_0002
Figure imgf000028_0002
Etape 1 : Synthèse du dibromure de 1 ,1 '-(disulfanediyldiéthane-2,1-diyl)bis(4- méthyl-pyridinium)Step 1: Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4-methylpyridinium) dibromide
67 g de 4-picoline sont dilués dans 100 ml_ d'acétonitrile et le mélange est porté à67 g of 4-picoline are diluted in 100 ml of acetonitrile and the mixture is brought to
80 0C. Un mélange de 60 g de 1-bromo-2-[(2-bromoéthyl)disulfanyl]éthane et 15 mL de80 0 C. A mixture of 60 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane and 15 ml of
N-méthylpyrrolidinone (NMP) est ajouté en 5 min. Après 4 h d'agitation à 85 0C, le mélange est refroidi. Le solide obtenu est filtré, rincé par 3 x 200 mL d'acétonitrile puis dissout dans 800 mL d'isopropanol à reflux. Après refroidissement, 1 L d'éther éthylique est ajouté. Le précipité formé est filtré, rincé par 3 x 200 ml_ d'éther éthylique puis séché. Poudre blanc (73,77g).N-methylpyrrolidinone (NMP) is added in 5 min. After stirring for 4 h at 85 ° C., the mixture is cooled. The solid obtained is filtered, rinsed with 3 x 200 mL of acetonitrile and then dissolved in 800 mL of isopropanol at reflux. After cooling, 1 L of ether ethyl is added. The precipitate formed is filtered, rinsed with 3 × 200 ml of ethyl ether and then dried. White powder (73.77g).
Etape 2 : Synthèse du dibromure de 1 ,1 '-(disulfanediyldiéthane-2,1-diyl)bis(4- {(E)-2-[4-(diméthylamino)phényl]vinyl}pyridinium) [II]Step 2: Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4- {(E) -2- [4- (dimethylamino) phenyl] vinyl} pyridinium dibromide [II]
13,2 g de 4-diméthylaminobenzaldéhyde sont mis en suspension dans 100 ml_ de méthanol. 6,2 g de pyrrolidine puis 5.3 g d'acide acétique dilués dans 20 m L de méthanol sont ajoutés au mélange (pH final 5/6). 20 g de dibromure de 1 ,1'- (disulfanediyldiéthane-2,1-diyl)bis(4-méthylpyridinium) obtenus à l'étape précédente, solubilisés dans 80 m L de méthanol sont introduits, puis le mélange réactionnel est dilué par ajout de 100 ml_ de méthanol. Après 21 h d'agitation à température ambiante, un premier précipité est recueilli, lavé par 3 x 100 ml_ d'éthanol puis 3 x 200 ml_ d'acétate d'éthyle et séché (poudre rouge, 7,4 g), puis un second précipité formé dans le filtrat est également recueilli et séché (poudre rouge, 11 ,44 g). Les analyses indiquent que les deux fractions sont conformes à la structure attendue.13.2 g of 4-dimethylaminobenzaldehyde are suspended in 100 ml of methanol. 6.2 g of pyrrolidine then 5.3 g of acetic acid diluted in 20 ml of methanol are added to the mixture (final pH 5/6). 20 g of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4-methylpyridinium) dibromide obtained in the preceding step, solubilized in 80 ml of methanol, are introduced and the reaction mixture is then diluted by addition. 100 ml of methanol. After stirring for 21 h at room temperature, a first precipitate is collected, washed with 3 x 100 ml of ethanol then with 3 x 200 ml of ethyl acetate and dried (red powder, 7.4 g), then The second precipitate formed in the filtrate is also collected and dried (red powder, 11.44 g). The analyzes indicate that both fractions are consistent with the expected structure.
RMN 1H (400 MHz, MeOH-Of4) : 3.02 (s, 12 H), 3.42 (t, 4 H), 4.74 (t, 4 H), 6.77 (d, 4 H), 7.19 (d, 2 H), 7.6 (d, 4 H), 7.97 (d, 2 H), 8.1 (d, 4 H), 8.79 (d, 4 H). 1 H NMR (400 MHz, MeOH-Of 4): 3.02 (s, 12H), 3.42 (t, 4H), 4.74 (t, 4H), 6.77 (d, 4H), 7.19 (d, 2 H), 7.6 (d, 4H), 7.97 (d, 2H), 8.1 (d, 4H), 8.79 (d, 4H).
Synthèse du bromure de 4-{(E)-2-[4-(diméthylamino)phényl]vinyl}-1-(2-sulfanyl- éthyl)pyridinium [I]Synthesis of 4 - {(E) -2- [4- (dimethylamino) phenyl] vinyl} -1- (2-sulfanylethyl) pyridinium bromide [I]
Figure imgf000029_0001
Figure imgf000029_0001
Schéma de synthèse Diagram of synthesis
Figure imgf000030_0001
Figure imgf000030_0001
90 mg du composé [II] sont dissous dans 10 mL de mélange eau/éthanol 1 : 1 ; 60 mg (2 éq.) d'hydrate de chlorhydrate d'acide 3-[bis(2-carboxy-éthyl)phosphino]- propanoïque en solution dans 1 mL d'eau et 21 mg (4 éq) de bicarbonate de sodium en solution dans 1 mL d'eau sont ajoutés au mélange. Après 30 minutes d'agitation à 400C sous atmosphère inerte, les analyses indiquent que le mélange contient très majoritairement le produit attendu [I].90 mg of the compound [II] are dissolved in 10 mL of water / ethanol 1: 1; 60 mg (2 eq) of 3- [bis (2-carboxyethyl) phosphino] propanoic acid hydrochloride hydrate in solution in 1 mL water and 21 mg (4 eq) sodium bicarbonate solution in 1 mL of water are added to the mixture. After stirring for 30 minutes at 40 ° C. under an inert atmosphere, the analyzes indicate that the mixture contains most of the expected product [I].
Analyse LC-MS : LC-DAD (400-700 nm) Colonne : Waters XTerra MS C18 5μm (4.6 x 50) mmLC-MS analysis: LC-DAD (400-700 nm) Column: Waters XTerra MS C18 5μm (4.6 x 50) mm
Phase Mobile : A : Eau + acide formique 0.1% / B : acétonitrileMobile phase: A: Water + formic acid 0.1% / B: acetonitrile
Gradient linéaire : T (min) A%/B% : 0 min 95/5 ; 8 min 0/100Linear gradient: T (min) A% / B%: 0 min 95/5; 8min 0/100
Débit : 1mL/min.Flow: 1mL / min.
Détection : UV Barrette de diodes λ=400-700nm Temps de rétention t = 4.3 min.Detection: UV Diode array λ = 400-700nm Retention time t = 4.3 min.
Pureté relative > 90%Relative purity> 90%
MS (ESI+) m/z= 285 correspond au pic de masse du monocation du produit attendu [I] EXEMPLES DE COLORATIONMS (ESI +) m / z = 285 corresponds to the mass peak of the expected product monocation [I] EXAMPLES OF COLORING
Procédé de coloration avec composé [I]Staining method with compound [I]
10 m L de solution fraîche du composé [I] ou [II] des exemples de synthèse sont appliqués sur une mèche de 1 g de cheveux de hauteur de ton 4 disposées au fond d'un même bol pendant 30 minutes à température ambiante (les mèches sont retournées et réimprégnées après 15 minutes). Les mèches sont ensuite rincées à l'eau courante et séchées.10 ml of fresh solution of the compound [I] or [II] of the synthetic examples are applied to a lock of 1 g of hair of pitch 4 arranged at the bottom of the same bowl for 30 minutes at room temperature (the wicks are returned and re-impregnated after 15 minutes). The locks are then rinsed with running water and dried.
Après coloration, la mèche de hauteur de ton 4 est devenue visuellement plus claire que des mèches témoins non traitées.After staining, the pitch lock 4 became visually brighter than untreated control locks.
Procédé de coloration avec composé [II]Staining method with compound [II]
Préparation d'une composition APreparation of a composition A
Colorant disulfure de [1] à [3] 10"3 mol%Disulfide dye from [1] to [3] 10 -3 mol%
Alcool Benzylique 4 gBenzyl alcohol 4 g
Polyéthylèneglycol 6OE 6 gPolyethylene Glycol 6OE 6 g
Hydroxyethyl cellulose 0,7 gHydroxyethyl cellulose 0.7 g
Alkylpolyglucoside en solution aqueuse à 65%MA 4.5 gAlkylpolyglucoside in 65% aqueous solution MA 4.5 g
Eau déminéralisée qsp 100gDemineralized water qs 100g
Préparation d'une composition BPreparation of a composition B
Acide thioglycolique 1 MThioglycolic acid 1 M
Hydroxyde de Sodium qsp pH 8,5Sodium hydroxide qsp pH 8.5
Eau déminéralisée qsp 100gDemineralized water qs 100g
Au moment de l'emploi, on mélange les compositions A (9 mL) et B (1 mL), puis on applique le mélange obtenu sur une mèche de 1 g de cheveux foncés (hauteur de ton 4) pendant 30 minutes à température ambiante(les mèches sont retournées et réimprégnées après 15 minutes).At the time of use, compositions A (9 ml) and B (1 ml) are mixed, and then the mixture obtained is applied to a lock of 1 g of dark hair (pitch 4) for 30 minutes at room temperature. (The locks are returned and re-impregnated after 15 minutes).
Après rinçage à l'eau courante et séchage, on observe un éclaircissement des cheveux ainsi traités : la mèche de hauteur de ton 4 est devenue visuellement plus claire que des mèches témoins non traitées. Rémanence vis-à-vis des shampooings successifs :After rinsing with running water and drying, a lightening of the hair thus treated is observed: the lock of pitch 4 became visually clearer than untreated control locks. Remanence vis-à-vis successive shampoos:
Les mèches ainsi traitées sont divisées en deux, une moitié est soumise à 5 shampooings successifs selon un cycle qui comprend le mouillage des mèches à l'eau, le lavage avec un shampooing classique, un rinçage à l'eau suivi d'un séchage.The locks thus treated are divided in two, one half is subjected to 5 successive shampoos in a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water followed by drying.
Observations visuellesVisual observations
Lors des shampooings, il n'y a pas de dégorgement visible, la mousse des shampooings et les eaux de rinçage ne sont pas coloréesDuring shampoos, there is no visible bleeding, shampoo foam and rinsing water are not colored
La couleur observée est conservée et l'effet d'éclaircissement reste visible sur les cheveux de hauteur de ton 4 ainsi traités.The observed color is preserved and the lightening effect remains visible on the hair of pitch 4 thus treated.
Résultats dans le système L*a*b* :Results in the L * a * b * system :
La couleur des mèches avant et après les 5 lavages a été évaluée dans le systèmeThe color of the locks before and after the 5 washes was evaluated in the system
L*a*b* au moyen d'un spectrophotomètre CM 2600 KONICA MINOLTA ®, (Illuminant D65).L * a * b * using a KONICA MINOLTA ® CM 2600 Spectrophotometer, (Illuminant D65).
Dans ce système L* a* b*, L* représente l'intensité de la couleur, a* indique l'axe de couleur vert/rouge et b* l'axe de couleur bleu/jaune. Plus la valeur de L est élevée, plus la couleur est claire ou peu intense. Inversement, plus la valeur de L est faible, plus la couleur est foncée ou très intense. La variation de la coloration entre les mèches de cheveux de HT 4 et les mèches de cheveux après traitement (coloration, ou coloration et lavages successifs) est mesurée par ΔE selon l'équation suivante :In this system L * a * b *, L * represents the intensity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The higher the L value, the lighter or less intense the color. Conversely, the lower the value of L, the darker or more intense the color. The variation of the color between the locks of hair of HT 4 and the locks of hair after treatment (coloration, or coloration and successive washings) is measured by ΔE according to the following equation:
Δ E = V(L* - L0 *)2 + (a* - a0 *)2 + (b* - b0 *)2 ΔE = V (L * - L 0 * ) 2 + (a * - a 0 * ) 2 + (b * - b 0 * ) 2
Dans cette équation, L*, a* et b* représentent les valeurs mesurées après traitement et L0*, ao* et bo* représentent les valeurs mesurées avant traitement.In this equation, L *, a * and b * represent the values measured after treatment and L 0 *, ao * and bo * represent the values measured before treatment.
Figure imgf000032_0001
Figure imgf000033_0002
Figure imgf000032_0001
Figure imgf000033_0002
Les résultats du tableau montrent qu'il n'existe pas d'écart significatif de variation de couleur même après 5 shampooings. Ainsi la coloration et l'effet éclaircissant sur les cheveux restent quasiment inchangés ce qui montre une très bonne résistance aux shampooings des colorants de l'invention.The results of the table show that there is no significant difference in color variation even after 5 shampoos. Thus the coloration and the lightening effect on the hair remain virtually unchanged which shows a very good resistance to shampoos dyes of the invention.
Résultats de Réflectance :Reflectance results:
Les performances d'éclaircissement des compositions conformes à l'invention et leur rémanence vis-à-vis de shampooings successifs ont été exprimées en fonction de la réflectance des cheveux. Ces réflectances sont comparées à la réflectance d'une mèche de cheveux non traitée de hauteur de ton HT4.The lightening performance of the compositions according to the invention and their persistence with respect to successive shampoos were expressed as a function of the reflectance of the hair. These reflectances are compared to the reflectance of an untreated strand of HT4 pitch hair.
La réflectance est mesurée au moyen d'un appareil spectrophotocolorimètre KONIKA- MINOLTA ®, CM 260Od et après irradiation des cheveux avec une lumière visible dans la gamme de longueurs d'onde allant de 400 à 700 nanomètres.The reflectance is measured using a KONIKA-MINOLTA®, CM 260Od spectrophotocolorimeter and after irradiation of the hair with visible light in the wavelength range of 400 to 700 nanometers.
Fig. 1Fig. 1
Réflectance des mèches traitées par le composé (I) à l'application et après 5 shampooingsReflectance of wicks treated with compound (I) at application and after 5 shampoos
- 5 shampooings- 5 shampoos
Figure imgf000033_0001
o O oCM o-^ otD oOO oO oCM orJ- oCD oOO oO oCM orJ- oCD oOO oO
Figure imgf000033_0001
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
-* -<* (O CD !•«-- * - <* (O CD! • « -
Longueur d'onde (nm) Fig. 2Wavelength (nm) Fig. two
Figure imgf000034_0001
Figure imgf000034_0001
D'après les figures 1 et 2 on constate tout d'abord que la réflectance d'une mèche de cheveux traitée avec une composition selon l'invention colorant [I] est supérieure à celle des cheveux non traités. Les mèches traitées apparaissent donc plus claires.From Figures 1 and 2 it is firstly noted that the reflectance of a lock of hair treated with a composition according to the invention dye [I] is greater than that of untreated hair. The treated locks therefore appear clearer.
De plus, les résultats montrent que la réflectance des mèches de cheveux de hauteur de ton 4 traitées avec la composition de l'invention évoluent très peu après 5 shampooings. Ainsi la coloration et l'effet éclaircissant sur les cheveux restent quasiment inchangés ce qui montre une très bonne résistance aux shampooings des colorants de l'invention. In addition, the results show that the reflectance of the locks of hair of pitch 4 treated with the composition of the invention evolve very little after shampooing. Thus the coloration and the lightening effect on the hair remain virtually unchanged which shows a very good resistance to shampoos dyes of the invention.

Claims

REVENDICATIONS
1. Colorant fluorescent de formule (I) suivante :1. Fluorescent dye of formula (I) below:
Figure imgf000035_0001
ses sels d'acide organique ou minéral, isomères optiques, isomères géométriques, et les solvates tels que hydrates ; formule (I) dans laquelle :
Figure imgf000035_0001
its organic or inorganic acid salts, optical isomers, geometric isomers, and solvates such as hydrates; formula (I) in which:
> Y représente i) un métal alcalin ; ii) un métal alcalino-terreux ; iii) un groupement ammonium : N+F^R13R7R5 ou un groupement phosphonium : p+RαR β R γ R δ avec Rα R β R γ et R δ identiques ou différents, représentant un atome d'hydrogène ou un groupe (Ci-C4)alkyle ; ou iv) un groupement protecteur de fonction thiol ; etY represents i) an alkali metal; ii) an alkaline earth metal; iii) an ammonium group: N + F 1 R 13 R 7 R 5 or a phosphonium group: p + R α R β R γ R δ with R α R β R γ and R δ identical or different, representing an atom of hydrogen or a (C 1 -C 4 ) alkyl group; or iv) a thiol protecting group; and
> An" représente un contre-ion anionique ; étant entendu que :> An " represents an anionic counterion, it being understood that:
- lorsque le composé de formule (I) contient d'autres parties cationiques, il se trouve associé à un ou plusieurs contre-ions anioniques permettant d'atteindre l'électroneutralité de la formule (I).- When the compound of formula (I) contains other cationic parts, it is associated with one or more anionic counter-ions to achieve the electroneutrality of formula (I).
2. Colorant fluorescent de formule (I) selon la revendication précédente dans lequel Y représente un métal alcalin.2. Fluorescent dye of formula (I) according to the preceding claim wherein Y represents an alkali metal.
3. Colorant fluorescent de formule (I) selon la revendication 1 dans lequel Y représente un groupement protecteur.3. Fluorescent dye of formula (I) according to claim 1 wherein Y represents a protective group.
4. Colorant fluorescent de formule (I) selon la revendication précédente dans lequel Y représente un groupement protecteur choisi parmi les radicaux suivants :4. Fluorescent dye of formula (I) according to the preceding claim wherein Y represents a protective group chosen from the following radicals:
> (CrC4)alkylcarbonyle ;(C r C 4 ) alkylcarbonyl;
> (CrC4)alkylthiocarbonyle ; > (CrC4)alcoxycarbonyle ;(CrC 4 ) alkylthiocarbonyl; (C r C 4 ) alkoxycarbonyl;
> (CrC4)alcoxythiocarbonyle ;(CrC 4 ) alkoxythiocarbonyl;
> (CrC4)alkylthio-thiocarbonyle ;(CrC 4 ) alkylthiothiocarbonyl;
> (di) (CrC4) (alkyl)aminocarbonyle ;(di) (CrC 4 ) (alkyl) aminocarbonyl;
> (di) (CrC4) (alkyl)aminothiocarbonyle ; > arylcarbonyle ;> (di) (CrC 4 ) (alkyl) aminothiocarbonyl; >arylcarbonyl;
> aryloxycarbonyle ; > aryl(Ci-C4)alcoxycarbonyle ;>aryloxycarbonyl; > Aryl (Ci-C 4) alkoxycarbonyl;
> (di) (CrC4) (alkyl)aminocarbonyle ;(di) (CrC 4 ) (alkyl) aminocarbonyl;
> (CrC4)(alkyl)arylaminocarbonyle ;> (CrC 4 ) (alkyl) arylaminocarbonyl;
> carboxy ; > SO3 " ; M+ avec M+ représentant un métal ou alors M+ et M' de la formule (I) sont absents ;>carboxy;> SO 3 " ; M + with M + representing a metal or else M + and M 'of the formula (I) are absent;
> aryle éventuellement substitué,optionally substituted aryl,
> hétéroaryle éventuellement substitué;optionally substituted heteroaryl;
> hétérocycloalkyle éventuellement substitué, éventuellement cat ionique,; > isothiouronium -C(NR'cR'd)=N+R'ΘR'f; An" avec R'c, R'd, R'Θ et R'f, identiques ou différents représentent un atome d'hydrogène ou un groupement alkyle ; et An" représente un contre-ion anionique;optionally substituted heterocycloalkyl, optionally cat ionic; > isothiouronium -C (NR ' c R' d ) = N + R ' Θ R'f; An "with R 'c, R' d, R and R' f, like or different, represent a hydrogen atom or an alkyl group; and An" represents an anionic ion-against;
> isothiourée -C(NR'cR'd)=NR'Θ; avec R'c, R'd et R'Θ tels que définis précédemment ; > (di)arylalkyle éventuellement substitué ;> isothiourea -C (NR ' c R' d ) = NR 'Θ; with R ' c , R' d and R ' Θ as defined above; optionally substituted (di) arylalkyl;
> (di)hétéroarylakyle éventuellement substitué ;(di) optionally substituted heteroarylalkyl;
> CR'1R'2R'3 avec R'1, R'2 et R'3 identiques ou différents, représentant un atome d'halogène ou un groupe choisi parmi :> CR ' 1 R' 2 R ' 3 with R' 1 , R ' 2 and R' 3, which may be identical or different, representing a halogen atom or a group chosen from:
• alkyle ; • alcoxy ;• alkyl; • alkoxy;
• aryle éventuellement substitué ;• optionally substituted aryl;
• hétéroaryle éventuellement substitué ;Optionally substituted heteroaryl;
> P(Z1)R"1R"2R"3 avec R"1, et R"2 identiques ou différents représentent un groupement hydroxy, alcoxy ou alkyle, R"3 représente un groupement hydroxy ou alcoxy, et Z1 représente un atome d'oxygène ou de soufre ;> P (Z 1 ) R " 1 R" 2 R " 3 with R" 1 , and R " 2 which are identical or different, represent a hydroxyl, alkoxy or alkyl group; R" 3 represents a hydroxyl or alkoxy group, and Z 1 represents an oxygen or sulfur atom;
> cyclique stériquement encombré tel que le groupe adamantyle ; etcyclic sterically hindered such as the adamantyl group; and
> alcoxy(CrC4)alkyle éventuellement substitué.> alkoxy (C r C 4 ) alkyl optionally substituted.
5. Colorant fluorescent selon la revendication précédente dans lequel Y représente un groupement protecteur choisi parmi : > (CrC4)alkylcarbonyle ;5. Fluorescent dye according to the preceding claim wherein Y represents a protective group chosen from:> (C r C 4 ) alkylcarbonyl;
> arylcarbonyle ;> arylcarbonyl;
> (CrC4)alcoxycarbonyle ;> (CrC 4 ) alkoxycarbonyl;
> aryloxycarbonyle ; > aryl(Ci-C4)alcoxycarbonyle ;>aryloxycarbonyl; > Aryl (Ci-C 4) alkoxycarbonyl;
> (di)(CrC4)(alkyl)aminocarbonyle ;(di) (CrC 4 ) (alkyl) aminocarbonyl;
> (CrC4)(alkyl)arylaminocarbonyle ;> (CrC 4 ) (alkyl) arylaminocarbonyl;
> aryle éventuellement substitué ;optionally substituted aryl;
> hétéroaryle monocyclique à 5 ou 6 chaînons ;monocyclic 5- or 6-membered heteroaryl;
> hétéroaryle bicyclique cationique à 8 à 11 chaînons ;8 to 11-membered cationic bicyclic heteroaryl;
> hétérocycle cationique de formule suivante :cationic heterocycle of following formula:
Figure imgf000037_0001
Figure imgf000037_0001
> isothiouronium -C(NH2)=N+H2; An"; > isothiourée -C(NH2)=NH ; et> isothiouronium -C (NH 2 ) = N + H 2 ; An " isothiourea -C (NH 2 ) = NH, and
> SO3 " ; M+ > SO 3 " ; M +
6. Colorant fluorescent thiol protégé de formule (I) selon l'une quelconque des revendications précédentes, choisi parmi les colorants :6. protected thiol fluorescent dye of formula (I) according to any one of the preceding claims, chosen from the dyes:
Figure imgf000037_0002
Figure imgf000037_0002
Figure imgf000037_0003
Figure imgf000037_0003
Figure imgf000037_0004
Figure imgf000037_0004
An" 2An"
Figure imgf000038_0001
An " 2An "
Figure imgf000038_0001
7 8 avec An", identiques ou différents, représentant un contre-ion anionique.7 8 with An " , identical or different, representing an anionic counterion.
7. Composition tinctoriale comprenant dans un milieu cosmétique approprié, un colorant fluorescent thiol de formule (I) tel que défini dans une quelconque des revendications 1 à 6.7. Dyeing composition comprising in a suitable cosmetic medium, a thiol fluorescent dye of formula (I) as defined in any one of claims 1 to 6.
8. Composition tinctoriale comprenant dans un milieu cosmétique approprié, comprenant i) au moins un colorant fluorescent thiol de formule (I) selon une quelconque des revendications 1 à 6, de formule (II) ou de formule (III) et ii) au moins un agent réducteur :8. dye composition comprising in a suitable cosmetic medium, comprising i) at least one fluorescent dye thiol of formula (I) according to any one of claims 1 to 6, of formula (II) or formula (III) and ii) at least a reducing agent:
Figure imgf000038_0002
avec An" représente un contre-ion anionique.
Figure imgf000038_0002
with An " represents an anionic counterion.
9. Composition tinctoriale selon la revendication précédente dans laquelle l'agent réducteur est choisi parmi, la cystéine, l'homocystéine, l'acide thiolactique, les sels de ces thiols, les phosphines, le bisulfite, les sulfites, l'acide thioglycolique, ainsi que ses esters, les borohydrures et leurs dérivés, les sels de sodium, lithium, potassium, calcium, ammoniums quaternaires ; le catécholborane.9. Dyeing composition according to the preceding claim wherein the reducing agent is chosen from: cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid, as well as its esters, borohydrides and their derivatives, the sodium, lithium, potassium, calcium and quaternary ammonium salts; catecholborane.
10. Composition selon l'une quelconque des revendications 7 à 9, dans laquelle le colorant fluorescent de formule (I), (II) ou (III) est présent en quantité comprise entre 0,001 et 50% en poids par rapport au poids total de la composition.10. Composition according to any one of claims 7 to 9, wherein the fluorescent dye of formula (I), (II) or (III) is present in an amount of between 0.001 and 50% by weight relative to the total weight of the composition.
11. Procédé de coloration de matières kératiniques consistant à appliquer sur les matières, une composition tinctoriale comprenant au moins un colorant fluorescent thiol de formule (I), selon une quelconque des revendications 1 à 6, ou un colorant de formule (II) tel que défini dans la revendication 8.11. A method for dyeing keratinous materials comprising applying to the materials, a dye composition comprising at least one fluorescent dye thiol of formula (I), according to any one of claims 1 to 6, or a dye of formula (II) as defined in claim 8.
12. Procédé de coloration selon la revendication précédente dans lequel on applique sur les matières kératiniques, consistant à appliquer une composition tinctoriale comprenant dans un milieu cosmétique au moins un colorant thiol de formule (II) exempt de réducteur.12. The method of dyeing according to the preceding claim wherein is applied to the keratin materials, comprising applying a dye composition comprising in a cosmetic medium at least one thiol dye of formula (II) free of reducing agent.
13. Procédé de coloration de matières kératiniques, selon la revendication 11 consistant à appliquer une composition tinctoriale comprenant dans un milieu cosmétique approprié, au moins un colorant fluorescent thiol de formule (I) tel que défini dans une quelconque des revendications 1 à 6, en présence d'un agent réducteur capable de réduire les liaisons disulfures des matières kératiniques.13. A method for dyeing keratinous materials, according to claim 11, comprising applying a dye composition comprising, in a suitable cosmetic medium, at least one thiol fluorescent dye of formula (I) as defined in any one of claims 1 to 6, presence of a reducing agent capable of reducing the disulfide bonds of keratin materials.
14. Procédé selon la revendication précédente dans lequel l'agent réducteur est appliqué avant ou après l'application du colorant fluorescent thiol.14. Method according to the preceding claim wherein the reducing agent is applied before or after the application of the thiol fluorescent dye.
15. Procédé de coloration de matières kératiniques consistant à appliquer en un temps sur lesdites matières une composition tinctoriale, comprenant dans un milieu cosmétique approprié : i) au moins un colorant fluorescent disulfure choisi parmi les colorants de formule15. A method for dyeing keratinous materials comprising applying in a time to said materials a dyeing composition, comprising in a suitable cosmetic medium: i) at least one fluorescent dye disulfide chosen from dyes of formula
(I) tel que défini dans une quelconques des revendications 1 à 6, (II) et (III) tel que défini dans la revendication 8 ; et ii) au moins un agent réducteur.(I) as defined in any one of claims 1 to 6, (II) and (III) as defined in claim 8; and ii) at least one reducing agent.
16. Procédé de coloration selon la revendication précédente dans lequel lorsque le colorant fluorescent thiol de formule (I) comprend un groupement Y de protection, l'application est précédée d'une étape de déprotection.16. The method of dyeing according to the preceding claim wherein when the thiol fluorescent dye of formula (I) comprises a protecting Y group, the application is preceded by a deprotection step.
17. Procédé de coloration de matières kératiniques selon les revendications 11 à 16 caractérisé en ce que les matières kératiniques sont des fibres kératiniques foncées possédant une hauteur de ton inférieure ou égale à 6.17. A method of dyeing keratin materials according to claims 11 to 16 characterized in that the keratin materials are dark keratinous fibers having a pitch of less than or equal to 6.
18. Procédé selon une quelconque des revendications 11 , 12, 16 et 17 dans lequel la composition tinctoriale comprend un agent oxydant.18. A method according to any one of claims 11, 12, 16 and 17 wherein the dye composition comprises an oxidizing agent.
19. Procédé selon l'une quelconque des revendications 11 à 17 comprenant une étape supplémentaire consistant à appliquer sur les fibres kératiniques un agent oxydant.19. A method according to any one of claims 11 to 17 comprising a further step of applying to the keratin fibers an oxidizing agent.
20. Dispositif à plusieurs compartiments dans lequel un premier compartiment contient une composition tinctoriale comprenant un colorant fluorescent de formule (I),20. Multi-compartment device in which a first compartment contains a dye composition comprising a fluorescent dye of formula (I),
(II) ou (III) tel que défini aux revendications 1 à 6 et 8, et un deuxième compartiment contient un agent réducteur capable de réduire les liaisons disulfures des matières kératiniques.(II) or (III) as defined in claims 1 to 6 and 8, and a second compartment contains a reducing agent capable of reducing the disulfide bonds of keratin materials.
21. Dispositif selon la revendication précédente comprenant un troisième compartiment qui contient un agent oxydant. 21. Device according to the preceding claim comprising a third compartment which contains an oxidizing agent.
22. Utilisation de composition tinctoriale comprenant dans un milieu cosmétique au moins un colorant fluorescent de formule (I), (II) ou (III) tel que défini aux revendications 1 à 6 et 8 pour la teinture de fibres kératiniques humaines foncées.22. Use of a dye composition comprising in a cosmetic medium at least one fluorescent dye of formula (I), (II) or (III) as defined in claims 1 to 6 and 8 for dyeing dark human keratin fibers.
23. Utilisation selon la revendication précédente pour l'éclaircissement des fibres kératiniques foncées. 23. Use according to the preceding claim for lightening dark keratin fibers.
24. Utilisation selon les revendications 22 ou 23 dans laquelle la composition tinctoriale appliquée est exempte de réducteur.24. Use according to claims 22 or 23 wherein the applied dye composition is free of reducing agent.
25. Utilisation selon les revendications 22 à 24 caractérisée en ce que les fibres kératiniques possèdent une hauteur de ton inférieure à 6. 25. Use according to claims 22 to 24 characterized in that the keratin fibers have a pitch of less than 6.
PCT/FR2007/051004 2006-03-24 2007-03-23 Dyeing composition containing a masked thiol fluorescent colorant comprising a dimethylamino group, with an internal cationic charge, and method for lightening keratin materials using said colorant and disulphide colorants WO2007110538A2 (en)

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FR0651035A FR2898903B1 (en) 2006-03-24 2006-03-24 DYEING COMPOSITION COMPRISING A FLUORESCENT DISULFIDE DYE, METHOD OF LIGHTENING KERATINIC MATERIALS FROM THAT COLORANT
FR0651035 2006-03-24
US79294106P 2006-04-19 2006-04-19
US60/792,941 2006-04-19
FR0753071A FR2912139B1 (en) 2007-02-05 2007-02-05 DYEING COMPOSITION COMPRISING A THERMAL FLUORESCENT COLOR WITH DIMHTYLAMINO GROUP MASK, WITH INTERNAL CATIONIC LOAD, METHOD OF CLEANING KERATINIC MATERIALS FROM THAT COLORANT
FR0753071 2007-02-05
US90036207P 2007-02-09 2007-02-09
US60/900,362 2007-02-09

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WO2012113720A2 (en) 2011-02-25 2012-08-30 L'oreal Composition for dyeing keratinous fibres comprising a direct dye having a disulphide/thiol functional group, a thickening polymer, an ethoxylated fatty alcohol and/or a nonionic surfactant, an alkaline agent and a reducing agent
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