WO2017093558A1 - Nouveaux colorants anioniques contenant un motif disulfure hétérocyclique, composition de colorant les comprenant et procédé de coloration des matières kératiniques humaines à l'aide de ces colorants - Google Patents

Nouveaux colorants anioniques contenant un motif disulfure hétérocyclique, composition de colorant les comprenant et procédé de coloration des matières kératiniques humaines à l'aide de ces colorants Download PDF

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Publication number
WO2017093558A1
WO2017093558A1 PCT/EP2016/079734 EP2016079734W WO2017093558A1 WO 2017093558 A1 WO2017093558 A1 WO 2017093558A1 EP 2016079734 W EP2016079734 W EP 2016079734W WO 2017093558 A1 WO2017093558 A1 WO 2017093558A1
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dyes
group
crc
chosen
formula
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PCT/EP2016/079734
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English (en)
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Aziz Fadli
Zhibo LIU
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L'oreal
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/04—Five-membered rings having the hetero atoms in positions 1 and 2, e.g. lipoic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4986—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with sulfur as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/103—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the naphthalene series

Definitions

  • the invention relates to the dyeing of keratin materials using anionic dyes containing a disulfide heterocyclic group of formulae (I).
  • the direct dyes that are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines and dyes of the azo, xanthene, acridine, azine or triarylmethane type.
  • a chemical bleaching process is performed.
  • This process consists in treating the keratin fibres, such as the hair, with a strong oxidizing system, generally constituted by hydrogen peroxide optionally combined with persalts, usually in an alkaline medium.
  • This bleaching system has the drawback of degrading keratin fibres and of impairing their cosmetic properties. Specifically, the fibres have a tendency to become coarse, more difficult to disentangle and more brittle. Finally, the lightening or bleaching of keratin fibres with oxidizing agents is incompatible with treatments for changing the shape of said fibres, particularly in relaxing treatments.
  • Another lightening technique consists in applying to dark hair fluorescent direct dyes. This technique, described in particular in documents WO 03/028 685 and WO 2004/091 473, makes it possible to respect the quality of the keratin fibre during the treatment. However, these fluorescent direct dyes do not have sufficient fastness with respect to external agents.
  • carboxylic dyes comprising a disulfide heterocycle (A) and(B) (see formulae hereinafter) have been used and evaluated respectively as SERS (Surface Enhanced Raman Scattering) for detecting specific DNA sequences (Tetrahedron, 68(4), 1230-1240 (2012)) and as SAMs (Self Assembled Monolayers) on gold. These compounds have not been used for cosmetic purposes.
  • SERS Surface Enhanced Raman Scattering
  • SAMs Self Assembled Monolayers
  • the aim of the present invention is to provide novel systems for dyeing and/or lightening keratin materials, in particular human keratin fibres, such as the hair, which are powerful and long-lasting.
  • one aim of the invention is to provide direct dyeing systems for obtaining colours and/or lightening effects which are fast with respect to successive washing, which do not degrade the keratin materials and which do not impair their cosmetic properties. It is also sought to obtain a good colour build-up after treatment of the keratin materials.
  • Another aim of the invention is to dye keratin materials in a manner that is chromatic, strong and/or persistent with respect to external attacking factors.
  • the invention is also directed towards providing compounds for dyeing keratin fibres such as the hair with little colouration selectivity between the root and the end, whether it is performed on natural or permanent-waved fibres.
  • Het represents a 4- to 10-membered disulfide monocyclic heterocyclic radical
  • X and X' which may be identical or different, represent:
  • Ci-Ci 6 hydrocarbon-based chain optionally interrupted and/or optionally terminated at one or two of its ends with one or more divalent groups or combinations thereof chosen from: - -N(R)-; -0-; -S-; -C(O)-; -S(0) 2 - with R, which may be identical or different, being chosen from a hydrogen atom and a Ci-C 4 alkyl or d-C 4 hydroxyalkyl radical;
  • heterocyclic radical optionally comprising one or more identical or different heteroatoms, optionally substituted
  • o a divalent group or the combination chosen from: -N(R)-; -0-; -S-; -C(O)-; - S(0) 2 - with R as defined previously;
  • the divalent group(s) or combinations thereof are chosen from -0-;
  • p and p' which may be identical or different, represent an integer equal to 0 or 1 ;
  • Csat represents a linear or branched, saturated or unsaturated, optionally substituted Ci-Ci 6 hydrocarbon-based chain.
  • Another subject of the invention is a dye composition
  • a dye composition comprising, in a suitable cosmetic medium, at least one anionic direct dye containing a disulfide heterocyclic group of formula (I) as defined previously.
  • Another subject of the invention relates to the anionic direct dyes containing a disulfide heterocyclic group of formula (I) as defined previously, it being understood that the compound of formula (I) cannot represent the carboxylate forms of the compounds (A) or (B):
  • the process of the invention makes it possible to obtain a visible colouration of keratin materials, even dark keratin materials, in particular human keratin fibres, in particular the hair, without damaging said material, and that is persistent with respect to shampooing, common attacking factors (sunlight or perspiration), and other hair treatments, even in the absence of a reducing agent.
  • the process of the invention also makes it possible to obtain a lightening of keratin materials such as keratin fibres, particularly dark keratin fibres and more particularly dark hair.
  • the dyes, the composition and the process of the invention make it possible to improve the colour of keratin materials, in particular in terms of chromaticity, intensity and/or build-up of the colour.
  • the dyes of the invention are moreover stable with respect to oxidizing agents, and show satisfactory solubility in cosmetic dyeing media. These dyes extend the colour range to yellows and oranges.
  • the dyes of formula (I) colour the keratin materials, after application to keratin fibres, in a manner that is chromatic and persistent with respect to external attacking factors with low colouration selectivity between the root and the end, and on various types of fibres.
  • the expression "naturally or artificially dark hair” is intended to mean hair of which the tone depth is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut-brown).
  • the lightening of the hair is evaluated by the "tone depth” variation before and after application of the compound of formula (I).
  • tone is based on the classification of natural shades, one tone separating each shade from the shade immediately following or preceding it. This definition and the classification of natural shades are well known to hairstyling professionals and are published in the book “Sciences des.s capillaires [Hair treatment sciences]” by Charles Zviak, 1988, published by Masson, pp. 215 and 278.
  • the tone depths range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the figure, the lighter the shade.
  • the term "bleached hair” is intended to mean hair of which the tone depth is greater than 4 (chestnut-brown) and preferably greater than 6 (dark blond).
  • One means for measuring the lightening effect given to the hair after application of the fluorescent dyes of the invention is to use the phenomenon of reflectance of the hair.
  • the composition should, after application to dark hair, lead to the results below.
  • the curve corresponding to the treated hair should show a reflectance in the wavelength range from 500 to 700 nanometres higher than the curve corresponding to the untreated hair.
  • the wavelength at which the difference is maximal between the reflectance curve for the treated hair and that for the untreated hair is in the wavelength range from 500 to 650 nanometres and preferably in the wavelength range from 550 to 620 nanometres.
  • aryl or heteroaryl radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from:
  • Ci-C 8 alkyl radical optionally substituted with one or more radicals chosen from the radicals hydroxyl, CrC 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, acylamino, amino substituted with two identical or different d-C 4 alkyl radicals which optionally bear at least one hydroxyl group or it being possible for the two radicals to form, with the nitrogen atom to which they are attached, a saturated or unsaturated and optionally substituted 5- to 7-membered and preferably 5- or 6-membered heterocycle optionally comprising another nitrogen or non- nitrogen heteroatom;
  • halogen atom such as chlorine, fluorine or bromine
  • alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other nitrogen or non-nitrogen heteroatom,
  • an acylamino radical (-N(R)-C(0)R') in which the radical R is a hydrogen atom or a CrC 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a Ci-C 2 alkyl radical;
  • the carboxylic radical possibly being in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);
  • R represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a C1-C4 alkyl radical, or a phenyl radical;
  • R radicals which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group;
  • a polyhaloalkyl group preferentially trifluoromethyl (CF 3 ); the cyclic or heterocyclic part of a non-aromatic radical may be substituted with at least one substituent borne by a carbon atom, chosen from the groups:
  • alkylcarbonylamino (RC(O)-NR'-) in which the radical R' is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the radical R is a C C 2 alkyl radical or an amino radical substituted with two identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom;
  • alkylcarbonyloxy ((RC(O)-O-) in which the radical R is a C1-C4 alkyl radical or an amino radical substituted with two identical or different C1-C4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other nitrogen or non-nitrogen heteroatom;
  • alkoxycarbonyl ((RO-C(O)-) in which the radical R is a Ci-C 4 alkyl radical or an amino radical substituted with two identical or different d-C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other nitrogen or non-nitrogen heteroatom; a cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, may also be substituted with one or more oxo groups; a hydrocarbon-based chain is unsaturated when it comprises one or more double bonds and/or one or more triple bonds; an "aryl" radical represents a fused or non-fused monocyclic or polycyclic group containing from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is
  • cyclic radical is a non-aromatic, monocyclic or polycyclic, fused or non-fused cycloalkyi radical, containing from 5 to 22 carbon atoms, which may comprise one or more unsaturations;
  • a "heterocyclic radical” is a non-aromatic, monocyclic or polycyclic, fused or non- fused 5- to 22-membered radical, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, morpholinyl, thiomorpholinyl, piperidyl, piperazinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, azepanyl, thioazepanyl; preferentially pyrrolidinyl and morpholino;
  • a "disulfide heterocyclic radical” is a heterocyclic radical comprising in its ring an S-S disulfide sequence between two carbon
  • an ""alkoxy radical" is an alkyloxy radical for which the alkyl radical is a linear or branched Ci-Ci 6 and preferentially Ci-C 8 hydrocarbon-based radical; when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above.
  • the compounds of formula (I) according to the invention may be anionic, cationic or neutral;
  • the chromophore A is anionic; either it comprises one or more counterions or mixture of counterions in order to ensure electroneutrality, or else one or more group(s) in the compound make(s) it possible to ensure electroneutrality.
  • the rest of the compound is anionic via -O " , -C(0)0 " , S(0) 2 -0 " or -P(0)(OH) 2 -0 " groups, either there are in the molecule one or more— N + (R) 2 — , or phosphonium groups, in order to ensure electroneutrality, or it is in the form -
  • M + representing a cationic counterion, preferentially chosen from alkali metal or alkaline-earth metal cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH 4 + or (di/tri)(C 1 - C 6 )alkylammonium;
  • an "organic or mineral acid salt” is more particularly chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 S0 4 , iv) alkylsulfonic acids: Alk-S(0) 2 OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(0) 2 OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-0-S(0)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii)
  • anionic chromophore is intended to mean a radical derived from an anionic direct dye.
  • An anionic direct dye is a compound which is capable of absorbing in the visible range and optionally in the ultraviolet range, i.e. at a wavelength between 250 and 800 nm.
  • the chromophore may also be fluorescent, i.e. it is capable of absorbing in the visible range and optionally in the ultraviolet range and it is also capable of re-emitting the absorbed light in the visible range at an emission wavelength greater than the absorption wavelength, i.e. e m between 400 and 800 nm.
  • the fluorescent chromophore is derived from a fluorescent dye capable of absorbing in the visible range between 400 and 800 nm and of re-emitting in the visible range e m between 400 and 800 nm.
  • the fluorescent chromophore is derived from a dye capable of absorbing at a between 420 nm and 550 nm and of re-emitting in the visible range at a e m between 470 and 600 nm.
  • the dye(s) of formula (I) are anionic, i.e. the radical A of formula (I) contains one or more anionic chromophores, which may be identical or different, it being understood that, when A comprises several chromophores, it comprises more anionic chromophores than cationic chromophores. Preferably, all the chromophores of A are anionic. /.1. Anionic chromophore A
  • the dyes of the invention of formula (I) are anionic direct dyes.
  • the anionic chromophore(s) of the invention is (are) derived from anionic direct dyes called "acid dyes" for their affinity with alkaline substances (see, for example, “Industrial Dyes, Chemistry, Properties, Application”, Klaus Hunger published by Wiley-VCH Verlag GmbH & CoKGaA, Weinheim 2003).
  • Anionic or acid dyes are known in the literature (see, for example, Ullman's Encyclopedia of Industrial Chemistry, Azo Dyes, 2005 Wiley-VCH Verlag GmbH & Co.
  • anionic direct dyes is intended to mean any direct dye comprising in its structure at least one sulfonate S0 3 " group and/or at least one carboxylate group C(0)0 " and optionally one or more supplementary anionic groups G " with G " , which may be identical or different, representing an anionic group chosen from alkoxide O " , thiolate S “ , carboxylate and thiocarboxylate: C(Y)Y' " , with Y and Y', which may be identical or different, representing an oxygen or sulfur atom; preferably, G " represents a carboxylate, i.e. Y and Y represent an oxygen atom.
  • A represents a chromophore A1 :
  • ⁇ representing the anionic part of the chromophore derived from an anionic direct dye or acid dye comprising in its structure at least one sulfonate group and/or at least one carboxylate group and comprising m anionic charge(s):
  • ⁇ m and n which may be identical or different, represent an integer between 1 and 10 inclusive;
  • ⁇ Q + which may be identical or different, represents a cosmetically acceptable, organic or mineral, cationic counterion preferably chosen from alkali metal or alkaline-earth metal cations such as Na + or K + , or ammonium, (di)(tri)(Ci-
  • -Col ⁇ m comprises in its structure:
  • (hetero)aryl group preferentially aryl such as phenyl or benzo;
  • Col ⁇ m comprises in its structure:
  • At least one carboxylate group and at least one (hetero)aryl group, it being understood that at least one carboxylate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
  • -Col' " 'TM comprises in its structure:
  • At least one carboxylate group and at least one (hetero)aryl group it being understood that at least one sulfonate or carboxylate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
  • -Col' " 'TM comprises in its structure:
  • At least one carboxylate group, at least one sulfonate group and at least one (hetero)aryl group it being understood that at least one sulfonate or carboxylate group is directly connected to a (hetero)aryl group, preferentially aryl such as phenyl or benzo; and
  • the dyes of formula (I) are such that A represents A1 with m equal to n.
  • An advantageous variant of the invention concerns the dyes of formula (I) for which m and n are equal to 1 , 2 or 3.
  • the preferred dye(s) of formula (I) of the invention are chosen from those for which A is derived from acid nitro direct dyes, acid azo dyes such as diaryls or pyrrazolones, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid xanthene dyes, acid anthraquinone dyes, acid quinoline dyes, indigoid dyes and acid natural dyes; each of these dyes having at least one sulfonate or carboxylate group with a cationic counterion as defined previously, more particularly between 1 and 5 sulfonate or carboxylate groups, preferably between 1 and 3 sulfonate or carboxylate groups.
  • the preferred dye(s) of formula (I) of the invention are chosen from those for which A is derived from direct dyes chosen from diaryl anionic azo dyes; pyrrazolone anionic azo dyes; anthraquinone anionic dyes; anionic nitro dyes; anionic triarylmethane dyes; anionic indigoid or indole derived dyes; and anionic quinoline dyes; each of these dyes having at least one sulfonate or carboxylate group with a cationic counterion as previously defined, more particularly between 1 and 5 sulfonate or carboxylate groups, preferably between 1 and 3 sulfonate or carboxylate groups; more preferentially, A is derived from diaryl anionic azo dyes.
  • dyes having the formula of diaryl anionic azo dyes By way of examples of dyes having the formula of diaryl anionic azo dyes, mention may be made of: Acid Red 1 , Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41 , Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1 , Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 1 13, Acid Blue 1 17, Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 , Food Black 2; Acid Red 1 1 1 , Acid Red 134 and Acid yellow 38.
  • A is an anionic fluorescent chromophore derived from anionic direct fluorescent dyes. Mention may be made of the following direct dyes: anionic triarylmethanes; anionic xanthene dyes and anionic quinoline dyes; each of these dyes having at least one sulfonate or carboxylate group with a cationic counterion as previously defined.
  • A is derived from a fluorescent dye which absorbs in the yellow, orange and red range.
  • C sat represents a linear or branched, optionally substituted, divalent Ci-Ci 6 hydrocarbon-based chain.
  • Substituents that may be mentioned include amino groups, (Ci-C 4 )alkylamino groups, (CrC 4 )dialkyl amino groups, or the group R a -Z a -C(Z b )- (in which Z a , Z b , which may be identical or different, represent an oxygen or sulfur atom or a group NR a ', and R a represents an alkali metal, a hydrogen atom or a C C 4 alkyl group and R a ' represents a hydrogen atom or a C C 4 alkyl group) preferably present on the carbon in the beta or gamma position relative to the atoms of the disulfide sequence -S-S- of the heterocycle Het.
  • C sa t represents a linear or branched, preferably linear, saturated or unsaturated, preferably saturated, divalent hydrocarbon- based chain comprising from 1 to 14 carbon atoms, preferably between 2 and 10, more preferentially between 3 and 6 carbon atoms, such as 4 carbon atoms.
  • T and T' which may be identical or different, represent one or more radicals or combinations thereof chosen from: -S(0) 2 -; -0-; -S-; -N(R)-; -C(O)-; with R representing a hydrogen atom, a Ci-C 4 alkyl radical, C C 4 hydroxyalkyl radical or an aryl(Ci-C 4 )alkyl radical; and a cationic or non-cationic, preferentially monocyclic heterocycloalkyl or heteroaryl radical, preferentially containing two heteroatoms (more preferentially two nitrogen atoms) and preferentially being 5- to 7-membered, more preferentially piperazinyl or piperidinyl;
  • T and T represent one or more radicals or combinations thereof chosen from -0-, -N(R)-, -C(O)-, with R chosen from a hydrogen atom and a Ci-C 4 alkyl radical;
  • indices t and t' which may be identical or different, are 0 or 1 ;
  • z is 0 or 1 .
  • Z represents:
  • M representing an anionic counterion as defined previously.
  • Het represents a 4- to 10-membered disulfide monocyclic heterocyclic radical.
  • Het is of formula (II) linked to the rest of the molecule by one of the substituents R 5 , R6, R7, Rs, Rsi or R 10 , or else said radical is linked to the rest of the molecule directly by one of the carbon atoms of the heterocycle radical in the alpha, beta position with respect to the disulfide sequence or, when q is 2 or 3, in the gamma position, in which case one of the substituents R 5 , R 6 , R 7 , R 8 , Rg or R 10 is absent:
  • R 5 , R 6 , Rg and R1 0 which may be identical or different, represent a hydrogen atom, or a group chosen from: i) (CrC 8 )alkyl, iii) hydroxyl, iv) (di)(Ci- C 8 )(alkyl)amino, v) (Ci-C 8 )alkoxy, particularly R 5 , R 6 , Rg and R1 0 represent a hydrogen atom or a (CrC 4 )alkyl group such as methyl, preferably R 5 , R6, Rg and R1 0 represent a hydrogen atom;
  • R 7 and R 8 which may be identical or different, represent a hydrogen atom, or a group chosen from: i) (Ci-C 8 )alkyl, iii) hydroxyl, iv) (di)(Ci- C 8 )(alkyl)amino, v) (Ci-C 8 )alkoxy; particularly R 7 and R 8 , are chosen from a hydrogen atom and a (CrC 4 )alkyl group such as methyl, preferably R 7 and R 8 represent a hydrogen atom;
  • R 5 and R 6 , R7 and R 8 , and/or R 9 and R10 form, together with the carbon atom which bears them, a carbonyl group;
  • ⁇ q represents an integer between 1 and 3 inclusive, particularly between 1 and 2;
  • R 7 and R 8 groups may be identical to or different from one another;
  • q is 1 ; and more particularly all the substituents R 5 to R10 represent a hydrogen atom.
  • Dyes of formula (I) or ( ⁇ : Another subject of the invention relates to the anionic direct dyes containing a disulfide heterocyclic group of formula (I) as defined, it being understood that the compounds of formula (I) cannot represent the carboxylate forms of the compounds (A) or (B):
  • the anionic direct dyes of the invention are chosen from the dyes of formulae (I'a) to (I'g) below:
  • A is as defined previously, in particular A is derived from acid nitro direct dyes, acid azo dyes such as diaryls or pyrrazolones, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid xanthene dyes, acid anthraquinone dyes, acid quinoline dyes, acid indigoid dyes and acid natural dyes; each of these dyes having at least one sulfonate or carboxylate group with a cationic counterion as defined previously, more particularly between 1 and 5 sulfonate or carboxylate groups, preferably between 1 and 3 sulfonate or carboxylate groups;
  • A is derived from diaryl anionic azo dyes comprising from 1 to 5 sulfonate or carboxylate groups, preferably between 1 and 3 sulfonate groups;
  • X and X' represent a divalent group or the combination chosen from: -N(R)-, -0-, -S-, -C(O)- and -S(0) 2 - with R as defined previously;
  • the divalent group(s) or combinations thereof are chosen from - 0-, -N(R)- and -C(O)- with R chosen from a hydrogen atom and a CrC 4 alkyl radical; more preferentially, X and X' represent an amide divalent group -N(R)-C(0)- or -C(0)-N(R)- with R representing a hydrogen atom or a Ci-C 4 alkyl radical;
  • p and p' which may be identical or different, represent an integer equal to 0 or 1 ; preferably, p is 1 and p' is 0; and
  • Csat is as defined previously, and preferably represents an unsubstituted, linear or branched C1-C1 0 , more preferentially C 2 -C 8 , better still C 3 -C 5 , such as C 4 , alkylene chain;
  • R 5 , R 6 , Rg and Rio as defined previously, particularly represent a hydrogen atom or a (Ci-C 4 )alkyl group such as methyl, preferably R 5 , R6, R9 and R1 0 represent a hydrogen atom;
  • R 7 and R 8 as defined previously, particularly represent a hydrogen atom or a (Ci-C 4 )alkyl group such as methyl, preferably R 7 and R 8 represent a hydrogen atom;
  • all the substituents R 5 to R1 0 represent a hydrogen atom.
  • the compounds of formula (I) of the invention are chosen from the compounds (I'a) and (I'b), more preferentially (I'a).
  • the anionic dyes of formula (I) of the invention are chosen from the following compounds (l"a) and (l"b):
  • X, X' , p, p', Csat, R5, R6, R7, Re, R9 and R10 are as defined previously for the compounds of formulae (I'a) to (I'g), q is 1 or 2, it being understood that when q is 2 then the R 7 and R 8 groups may be identical to or different from one another, preferably q is 1 ; preferably, p is 1 and p' is 0, R 5 to R1 0 represent a hydrogen atom, X represents an amide divalent group -N(R)-C(0)- or -C(0)-N(R)- with R representing a hydrogen atom or a C1-C4 alkyl radical; and C sa t represents an unsubstituted linear or branched, more preferentially linear, C1-C1 0 alkylene chain;
  • Ri and R 2 which may be identical or different, represent a group chosen from: i) hydroxyl, ii) thiol, iii) nitro, iv) optionally substituted (CrC 6 )alkyl, in particular (d- C 4 )alkyl such as methyl or ethyl, v) (CrC 6 )alkoxy, in particular (CrC 4 )alkoxy such as ethoxy or methoxy, vi) (CrC 6 )alkylthio, vii) halogen and viii) amino - NR a Rb with R a and R b , which may be identical or different, representing:
  • R a and R b form, with the nitrogen atom which bears them, a 5- to 8- membered, preferably 5- or 6-membered, saturated or unsaturated heterocycle,
  • said heterocycle possibly also:
  • R c representing a hydrogen atom or a (CrC 4 )alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl or hydroxyethyl, and/or
  • groups which may be identical or different, chosen from hydroxyl, (C1-C4) alkyl optionally substituted with one or more hydroxyl groups, (CrC 4 )alkyloxy such as ethoxy or methoxy, (di)(Ci-C 4 )(alkyl)amino, (di)hydroxy(Ci-C 4 )alkylamino;
  • Z and Z' which may be identical or different, represent a carboxylate group -C(0)0 " , M + or sulfonate group -S(0) 2 -0 " M + , with M + representing a cosmetically acceptable cationic counterion, preferentially chosen from alkali metal or alkaline-earth metal cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH 4 + , (di/tri)(Ci-C 6 )alkylammonium, a cationic heteroaryl such as pyridinium; preferentially, Z and Z' represent an -S(0) 2 -0 " M + group;
  • t and t' which may be identical or different, represent an integer between 0 and 5 inclusive, it being understood that z+z' is an integer greater than or equal to 1 ; in particular z+z' is an integer between 1 and 3 inclusive;
  • x is an integer between 0 and 5 inclusive
  • x' is an integer between 0 and 4 inclusive; ⁇ , which may be present or absent, represents a benzo ring; the ring is preferably absent;
  • the anionic dyes of formula (I) according to the invention are chosen from those of formula (l"b).
  • the dyes are chosen from those of formula (l'"b):
  • x represents an integer between 0 and 4 inclusive, particularly between 1 and 3, and preferably is equal to 0 or 1 ;
  • x' represents an integer between 0 and 3, particularly between 1 and 2, and preferably is equal to 1 ;
  • X represents an amide divalent group -N(R)-C(0)- or -C(0)-N(R)-, preferably -N(R)-C(0)- with R representing a hydrogen atom or a CrC 4 alkyl radical;
  • p 1 ;
  • t' represents an integer between 1 and 3 inclusive, such as 2;
  • Ri which may be identical or different, represents a group chosen from: i) hydroxyl, ii) nitro, iv) (CrC 6 )alkyl, in particular (CrC 4 )alkyl such as methyl or ethyl, v) (CrC 6 )alkoxy, in particular (d-C 4 )alkoxy such as ethoxy or methoxy, vi) (CrC 6 )alkylthio, in particular (CrC 4 )alkylthio such as ethylthio or methylthio, and vii) amino -NR a R b with R a and R b , which may be identical or different, representing:
  • R a and R b form, with the nitrogen atom which bears them, a 5- or 6- membered saturated heterocycle, said heterocycle possibly also:
  • R c representing a hydrogen atom or a (C C 4 )alkyl group optionally substituted with one or more hydroxyl groups, such as methyl, ethyl or hydroxyethyl, and/or
  • R 2 which may be identical or different, represents a group chosen from: i) hydroxyl, ii) thiol, iv) (CrC 6 )alkyl, in particular (CrC 4 )alkyl such as methyl or ethyl, v) (CrC 6 )alkoxy, in particular (CrC 4 )alkoxy such as ethoxy or methoxy, vi) (CrC 6 )alkylthio, in particular (CrC 4 )alkylthio such as ethylthio or methylthio, and vii) amino -NR a R b with R a and R b , which may be identical or different, representing a hydrogen atom, or a (CrC 6 )alkyl group, particularly (CrC 4 )alkyl group such as methyl or ethyl; preferably, R 2 represents a hydroxyl or thiol group, more preferentially thiol group
  • Z' which may be identical or different, represents an -S(0) 2 -0 " M + group with M + representing a cationic counterion, preferentially chosen from alkali metal or alkaline-earth metal cations such as Na, Mg, K and Ca, and organic cations such as ammonium NH 4 + or (di/tri)(Ci-C 4 )alkylammonium;
  • C sat represents a linear or branched, preferably linear, (d-C 8 )alkylene group, such as -(CH 2 ) m - with m representing an integer between 2 and 8 inclusive, in particular between 3 and 6, such as m is 4;
  • Ri is on the phenyl ring in position 2', 4' and/or 6', preferably in position 4';
  • R 2 is on the naphthyl ring in position 1 , 4, 5 and/or 8, preferably in position 8;
  • the group X is linked to the naphthyl ring in position 1 , 4, 5 and/or 8, preferably in position 1 , it being understood that X cannot be positioned on a position where there is an R 2 group;
  • Z' is on the naphthyl ring in position 2, 3, 6 and/or 7, preferably in position 3 and 6;
  • the dyes are chosen from those of formula (l""b):
  • x' is 0, 1 or 2, more particularly x' is 0;
  • R represents a hydrogen atom or a (CrC 4 )alkyl group; more preferentially, R represents a hydrogen atom;
  • R 2 is positioned in position 2 or 5 on the naphthyl ring.
  • R represents a hydrogen atom or a (CrC 4 )alkyl group; more preferentially, R
  • Ri represents a group chosen from i) hydroxyl, ii) nitro, iii) Ci-C 4 alkylthio such as methylthio, iv) CrC 4 , more preferentially CrC 2 , alkoxy, such as methoxy or ethoxy, v) amino NR a R b with:
  • R a and R b which may be identical or different, representing a hydrogen atom, a C C 4 alkyl group such as methyl or ethyl, or a CrC 4 , preferentially CrC 2 , hydroxyalkyl group such as hydroxyethyl; or else
  • heterocyde possibly also:
  • R o comprising one or more heteroatoms or groups chosen from an oxygen atom or -N(R C )- group, with R c representing a hydrogen atom or a CrC 4 alkyl group such as methyl, and/or
  • o being substituted with one or more groups, which may be identical or different, chosen from hydroxyl, CrC 4 alkyl, C1-C4 hydroalkyl, C1-C4 alkoxy, (di)(Ci-C 4 )(alkyl)amino and (di)hydroxy(Ci-C 4 )alkylamino groups; and
  • Csat denotes a saturated divalent hydrocarbon-based (or alkylene) chain containing from 2 to 8 carbon atoms, preferably from 3 to 6 carbon atoms.
  • anionic dyes of formula (I) are of formula (l'"b) with:
  • R represents a hydrogen atom
  • Ri represents a group chosen from i) hydroxyl, nitro (N0 2 ), iii) CrC 4 alkylthio such as methylthio, CrC 4 alkoxy such as methoxy or ethoxy, iv) amino NR a Rb with R a and R b independently representing a hydrogen atom, a CrC 4 alkyl group such as methyl or ethyl; a CrC 4 , more preferentially CrC 2 , hydroxyalkyl group, such as hydroxyethyl, or else R a and R b form, with the nitrogen atom which bears them, a 5- or 6-membered saturated heterocyde chosen from pyrrolidine, piperidine and piperazine rings, said heterocyde possibly also being substituted with one or more groups, which may be identical or different, chosen from hydroxyl groups, Ci-C 4 alkyl groups such as methyl, and CrC 4 hydroalkyl groups such as hydroxyethyl; Csat represents
  • anionic dyes of formula (I) are chosen from:
  • M + a cationic counterion as defined previously, preferably alkali metal such as Na or K, or ammonium or pyridinium;
  • the compounds (I) may be synthesized via a reaction between a compound (a1 ) and a compound (a1 ). This reaction is illustrated in the scheme below:
  • Carbodiimides Carboxylic acids N-Acylureas or
  • ** the acyl azides may rearrange to give isocyanates.
  • nucleophilic and electrophilic groups of the reagents that are not intended to react with one another before the condensation reaction. It is then necessary to deprotect said nucleophilic and electrophilic groups.
  • Amine-protecting, hydroxyl-protecting and thiol-protecting groups are well known to those skilled in the art, including the reaction conditions necessary for the protection and deprotection step. Reference may be made to the book Protecting groups in Organic Chemistry (ISBN 0-471 -05764-9) for the protection and deprotection conditions.
  • the compounds ( ) may be synthesized via a reaction between a compound (a3) and a compound (a4). This reaction is illustrated in the scheme below:
  • the compounds (I) may be synthesized via a reaction between a compound (a1 ) and a compound (a1 ). This reaction is illustrated in the scheme below:
  • the compounds (l 2 ) may be synthesized via a reaction between a compound (a5) and a compound (a6). This reaction is illustrated in the scheme below:
  • T a the bond generated after attack of the nucleophile on the electrophile.
  • T a the covalent bonds T a that may be generated are listed in Table B, starting with condensation of electrophiles with nucleophiles:
  • Alkyl halides Amines Alkylamines Alkyl halides Carboxylic acids Esters
  • Carbodiimides Carboxylic acids N-Acylureas or anhydrides
  • acyl azides may rearrange to give isocyanates.
  • the reagent (a10) can react with an anionic chromophore (a7) to give an anionic dye (l 3 ) according to the invention.
  • the compounds (a9) and (a10) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
  • the reagent (a12) can react with an anionic chromophore (a2) to give an anionic dye (l 3 ) according to the invention.
  • the compounds (a11 ) and (a12) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
  • Another subject of the invention is a cosmetic composition
  • a cosmetic composition comprising at least one anionic dye containing a disulfide heterocyclic group of formula (I) as defined previously.
  • the compound of formula (I) cannot represent the carboxylate forms of the compounds (A) or (B):
  • composition of the invention may also contain a reducing agent.
  • the composition does not contain any reducing agent.
  • the dye composition that is useful in the invention generally contains an amount of dye of formula (I) 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 preferentially between 0.01 % and 5% by weight relative to the total weight of the composition.
  • composition according to the invention may also contain additional direct dyes different from the dyes of formula (I).
  • direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
  • composition according to the invention may contain one or more oxidation bases and/or one or more couplers conventionally used for the dyeing of keratin fibres.
  • oxidation bases mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
  • couplers mention may be made in particular of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
  • the coupler(s) are each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.
  • the oxidation base(s) present in the dye composition are each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.
  • the addition salts of the oxidation bases and couplers that can be used in the context of the invention are in particular chosen from the salts of addition with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the salts of addition with a base, such as alkali metal hydroxides, for instance sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulf
  • the process of the invention does not involve any oxidation dye
  • the composition comprising the anionic dye(s) of formula (I) preferably does not contain any oxidation dye.
  • the dyeing process of the invention does not involve any oxidizing agent.
  • the composition comprising the anionic dye(s) of formula (I) of the invention preferably does not comprise any oxidizing agent.
  • composition according to the invention is cosmetic, i.e. it is in a cosmetic medium that is suitable for dyeing keratin materials, also called dye support, generally made up of water or of a mixture of water and at least one organic solvent.
  • organic solvent for example, of lower Ci-C 4 alkanols, such as ethanol and isopropanol, polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether or diethylene glycol monomethyl ether, and also aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents are preferably present in proportions preferably of between 1 % and 99% by weight approximately and even more preferentially between 5% and 95% by weight approximately relative to the total weight of the dye composition.
  • composition according to the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, non-ionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, non-ionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones such as amino silicones, film-forming agents, ceramides, preserving agents, opacifiers and conductive polymers.
  • adjuvants conventionally used in hair dye compositions, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, non-ionic, amphoter
  • the above adjuvants are generally present in an amount for each of them of between 0.01 % and 20% by weight relative to the weight of the composition.
  • the pH of the composition according to the invention is generally between 3 and 14 approximately and preferably between 5 and 1 1 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents regularly used in the dyeing of keratin fibres or alternatively using conventional buffer systems.
  • acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
  • basifying agents examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and also derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula ( ⁇ ) below:
  • W a is a propylene residue optionally substituted with a hydroxyl group or a Ci-C 4 alkyl radical;
  • R a i, R a 2, R a3 and R a4 which may be identical or different, represent a hydrogen atom or a C C 4 alkyl or d-C 4 hydroxyalkyl radical.
  • composition according to the invention may be in various forms, such as in the form of a liquid, a cream or gel, or in any other form that is suitable for dyeing keratin fibres, and in particular the hair.
  • Another subject of the invention is a process for dyeing and/or lightening keratin materials, in particular human keratin fibres such as the hair, consisting in applying to said materials a composition comprising at least one anionic dye of formula (I) as defined previously.
  • the process for dyeing and lightening dark keratin materials consists in applying to said materials a composition comprising at least one anionic dye of formula (I) which is fluorescent and preferably which absorbs in the yellow, orange and red range.
  • the anionic dyes of formula (I) comprise a chromophore A which is anionic and derived from anionic fluorescent dyes. Mention may be made of anionic triarylmethane fluorescent direct dyes; anionic xanthene dyes and anionic quinoline dyes; each of these dyes having at least one sulfonate or carboxylate group with a cationic counterion as previously defined.
  • A is derived from a fluorescent dye which absorbs in the yellow, orange and red range.
  • a reducing agent is applied before, at the same time as or after the application of the composition containing at least one anionic dye of formula (I) as defined previously.
  • the reducing agent is used in the process according to the invention before the application of the anionic dye(s) of formula (I).
  • the reducing agent is used at the same time as the anionic dye(s) of formula (I).
  • the anionic dye(s) of formula (I) is (are) in a cosmetic composition, a composition according to the invention, which also comprises the reducing agent. This composition is then applied to the keratin materials.
  • the composition containing at least one anionic dye of formula (I) is applied to the keratin materials, the composition is left on for a certain time, and then the keratin materials are rinsed, and/or drained dry and/or undergo a heat treatment, in particular with steam (steampod), and/or are exposed to ultraviolet (UV) light.
  • a heat treatment in particular with steam (steampod), and/or are exposed to ultraviolet (UV) light.
  • the duration of the treatment after application of the composition containing at least one anionic dye of formula (I) may be short, for example from 0.1 second to 1 hour, particularly between 5 minutes and 50 minutes and more particularly between 10 and 45 minutes, and preferentially the leave-on time is 30 minutes.
  • the duration of the post-treatment with heat may be short, for example from 0.1 to 30 minutes.
  • the temperature is between 40°C and 250°C, more particularly between 50°C and 200°C and preferentially from 80°C to 180°C.
  • the heat treatment of the keratin fibres is performed using an iron for smoothing keratin fibres or using a hairstyling hood, a hairdryer or an infrared ray dispenser.
  • the dyeing and/or lightening process according to the invention consists in applying the composition according to the invention to the keratin materials and then in draining them dry and/or subjecting them to a heat treatment particularly at a temperature of between 50 and 200°C and more preferentially between 80 and 180°C, with, for example, a smoothing iron.
  • a heat treatment particularly at a temperature of between 50 and 200°C and more preferentially between 80 and 180°C, with, for example, a smoothing iron.
  • the heat treatment is followed by rinsing.
  • the duration of the post-treatment with UV is between 1 second and 2 hours, preferentially 30 minutes.
  • One particular embodiment of the invention concerns a process in which the anionic direct dye of formula (I) may be applied directly to the hair without reducing agents, free of pretreatment or post-treatment reducing agents.
  • a treatment with an oxidizing agent may optionally be combined.
  • Any type of oxidizing agent that is conventional in the field may be used.
  • it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases 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 fibres before or after applying the composition containing at least one anionic direct dye of formula (I) as defined previously.
  • Another subject of the invention is a multi-compartment dyeing device or dyeing "kit” in which a first compartment contains a dyeing composition comprising at least one compound of formula (I) and a second compartment contains an oxidizing agent.
  • One of these compartments may also contain one or more other dyes of direct dye or oxidation dye type.
  • Another subject of the invention is a multi-compartment dyeing device or dyeing "kit” in which a first compartment contains a dyeing composition comprising at least one compound of formula (I) and a second compartment contains a reducing agent.
  • One of these compartments may also contain one or more other dyes of direct dye or oxidation dye type.
  • Each of the devices mentioned above may be equipped with a means making it possible to apply the desired mixture to the hair, for instance the devices described in patent FR 2 586 913.
  • the compounds of formula (I) and in particular those of formula (l'"b) can be obtained by reacting an acid halide, preferably acid chloride (b), with the derivative (c) in an aprotic, preferably polar, solvent in the presence of a base, such as THF, in the presence of pyridine.
  • an acid halide preferably acid chloride (b)
  • the derivative (c) in an aprotic, preferably polar, solvent in the presence of a base, such as THF, in the presence of pyridine.
  • the acid halide in particular the acid chloride (b)
  • the acid chloride (b) can be prepared by the standard methods known to those skilled in the art, for example by reacting the corresponding carboxylic acid with thionyl chloride in an anhydrous aprotic solvent.
  • the pentanoyi 5-(1 ,2-dithioian-3-yl) chloride used in the subsequent step is prepared according to the following procedure:
  • Step 2 Synthesis of dipotassium 5- ⁇ [5-(1,2-dithiolan-3-yl)pentanoyl]amino ⁇ -4-oxo-3-(2- phenylhydrazinylidene)-3,4-dihydronaphthalene-2, 7-disulfonate:
  • the dyeing evaluation is carried out according to various modes in one or two steps, with or without pre-treatment of the keratin fibre.
  • the colour of the locks was evaluated before successive dyeing / after successive dyeing.
  • the colour of the locks is measured with a Minolta CM2600d spectrocolorimeter (specular components included, 10° angle, illuminant D65) in the CIEL * a * b * system.
  • L * represents the intensity of the colour
  • a * indicates the green/red colour axis
  • L * , a * and b * represent the values measured after dyeing
  • L 0 * , a 0 * and bo * represent the values measured before dyeing
  • a lock of 1 g of 90% natural white hair (90 NW) is treated in two steps with i) 10 ml of solution derived from 9 ml of water, then ii) 1 ml of 10% (w/w) thioglycolic acid solution containing 50 mg of compound of Example 1 is applied to the hair and left on the hair for 20 minutes. The lock is then treated with an 8-volume aqueous hydrogen peroxide solution for 10 minutes.
  • the lock is washed with water and then with shampoo and finally dried with a hairdryer.
  • the colour obtained is aesthetic, chromatic and fast reddish-pink. In addition, the colour build-up is very good.
  • a lock of 1 g of 90% natural white hair is treated with 50 mg of Example 1 dissolved in 10 ml of water. This solution is applied to the lock of hair with a leave-on time of 30 minutes on a hot plate at a temperature of 37°C.
  • the colour of the hair is measured with co orimetry.

Abstract

L'invention concerne la coloration de matières kératiniques au moyen de colorants directs anioniques contenant un groupe disulfure hétérocyclique. L'invention concerne une composition de colorant comprenant un colorant fluorescent contenant un groupe disulfure hétérocyclique, ainsi qu'un procédé de coloration de matières kératiniques telles que les cheveux, mettant en œuvre ladite composition. De façon similaire, l'invention porte sur de nouveaux colorants contenant un groupe disulfure hétérocyclique et leurs utilisations dans la coloration de matières kératiniques. Cette composition permet d'obtenir un effet éclaircissant qui est particulièrement rapide et visible sur fibres kératiniques foncées. En outre, le procédé de coloration de matières kératiniques, la composition et les colorants anioniques de l'invention permettent d'obtenir des couleurs sur lesdites matières qui sont intenses et chromatiques et présentant une bonne formation de couleur.
PCT/EP2016/079734 2015-12-03 2016-12-05 Nouveaux colorants anioniques contenant un motif disulfure hétérocyclique, composition de colorant les comprenant et procédé de coloration des matières kératiniques humaines à l'aide de ces colorants WO2017093558A1 (fr)

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