Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • 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
  • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
  • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
• • 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
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
• • 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
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
• • 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
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
• • 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
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4966—Triazines or their condensed derivatives
• • 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

Definitions

• the subject of the invention is new direct heteroaromatic tri-core dyes, the dye compositions containing these dyes as well as the process for dyeing keratin fibers using them.
• the subject of the invention is heteroaromatic tri-core direct dyes comprising a pyridine nucleus.
• the conventional dyes which are used are in particular dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine azine, triarylmethane benzene type or natural dyes type.
• These dyes which are colored and coloring molecules having an affinity for the fibers are applied to the keratin fibers for a time necessary to obtain the desired coloration, then rinsed.
• the resulting colorings are particularly chromatic colors which are however temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and / or from the core of the fiber are responsible for their low dye power and their poor resistance to washing or perspiration.
• These direct dyes are also generally sensitive to light due to the low resistance of the chromophore vis-à-vis photochemical attacks and lead over time to a fading of the coloring of the hair.
• Patent application EP 1166754 describes a dye composition which comprises cationic azo phenazinium direct dyes.
• the object of the present invention is to provide new direct dyes which do not have the drawbacks of the prior art, in particular direct dyes making it possible to obtain dark shades, black to gray, which are light-stable and resistant. weathering, washing and perspiration, and furthermore stable in a conventional coloring medium.
• the object of the present invention is to provide black direct dyes making it possible to dye the hair in shades varying from gray to black, without the need to lighten the hair beforehand, as well as black direct dyes which while fading do not change color, for example by turning after the action of a wash, light or sweat towards shades with blue, purple, red, green reflections, etc.
• black direct dyes must allow the shade obtained during the first application to be retained after several applications.
• R'-i and R' 2 being as defined for R, and R 2 • i and R 2 represent independently of each other:
• a linear or branched CC 10 hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an atom of 'oxygen, nitrogen or sulfur or by an SO 2 group; Ri and R 2 not comprising a peroxide bond, nor of diazo or nitroso radicals, and R1 and R2 not being directly connected to the nitrogen atom by an oxygen, sulfur, nitrogen or SO 2 atom, - an onium radical Z, or R T and R 2 form together with the nitrogen atom to which they are attached a cycle of formula (II):
• halogen atom such as fluorine, chlorine, bromine
• a CC 4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, carboxy, dC 4 alkoxycarbonyl, alkyl (CC 4 ) amido (alkyl (CC 4 ) CONH-), alkyl (CC 4 ) carbamoyl ( alkyl (CC 4 ) NHCO-), a (kyl (CC 4 ) sulfonyl (alkyl (CC 4 ) SO 2 -), alkoxy in
• alkylsulfonamido radical ((C r C 4 ) SO 2 NH - alkyl)
• R ' 3 and R' 4 represent a hydrogen atom; a CC 4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CrC 4 alkoxy, amino, mono or di alkylamino, (CC 4 ) CO- alkyl, (CC 4 ) NHCO-, alkyl (C r C 4 ) SO 2 -,
• - n is an integer between 1 and 8
• - m is an integer between 0 and 3, preferably from 0 to 2
• - Y represents an oxygen atom, a radical CR ', a radical NR' 5 or a radical NR ' 6 R' 7 with
• R ' 5 which represents a hydrogen atom; a linear or branched CrC 10 hydrocarbon chain which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group; R's having no peroxide bond, nor diazo or nitroso radicals, and R ' 5 not being directly linked to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R' 6 and R ′ 7 which independently represent a linear or branched CC 10 hydrocarbon chain which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group; R ' 6 and R' 7 not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ' 6 and R' 7 not being directly linked to the nitrogen atom by an oxygen atom, of sulfur or nitrogen, i represents an aromatic heterocycle radical chosen from the following radicals
• Z 2 , Z 4 , Z 6 independently of one another represent a nitrogen atom, a radical CR 12 or NRn with the proviso that at least one of them represents a radical CR 12 and that it does not there may be more than 3 contiguous nitrogen atoms,
• Z 8 represents a nitrogen atom, a radical CR 15 ;
• R 7 , R 8 , R 9 , R10, Ru, R 12 , R 15 independently of one another represent a hydrogen atom
• the dye composition according to the present invention comprises, in a suitable medium, a compound of formula (I) below or one of its addition salts:
• a hydrogen atom - a linear or branched CC 10 hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy radicals, amino, carboxy, sulfonic or thiol; R ⁇ and R 2 not comprising a peroxide bond, nor of diazo or nitroso radicals, and R1 and R2 not being directly linked to the nitrogen atom by an oxygen, sulfur, nitrogen or SO 2 , - an onium radical Z, or
• halogen atom such as fluorine, chlorine, bromine
• CC 4 alkyl (CrC 4 ) amido (alkyl (C r C 4 ) CONH-), alkyl (CC) carbamoyl (alkyl (CC 4 ) NHCO-), alkyl (CC 4 ) sulfonyl (alkyl (CC 4 ) SO 2 -), alkoxy in CC 4 , alkyl (CC) sulfonamido (alkyl (CC) SO 2 NH-), alkyl (CC 4 ) sulfamoyl (alkyl (CC 4 ) NH SO 2 -), onium Z,
• R ' 3 and R' 4 identical or different, represent a hydrogen atom; a CC 4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CC alkoxy, amino, mono or di alkylamino, alkyl (CC 4 ) CO-, alkyl (C r C 4 ) NHCO-, alkyl ( CC 4 ) SO 2 -,
• - n is an integer between 1 and 8
• - m is an integer between 0 and 3, preferably from 0 to 2
• - Y represents an oxygen atom, a radical CR ', a radical NR' 5 or a radical NR ' 6 R' 7 with R ' 5 which represents a hydrogen atom; a linear or branched CC 10 hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ′ 5 not comprising a peroxide bond, nor of diazo or nitroso radicals, and R ′ 5 not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R ' 6 and R' 7 which independently represent a linear or branched C ⁇ -C 10 hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which
• Z 2 , Z 4 , Z 6 independently of one another represent a nitrogen atom, a radical CR 12 or NR-H provided that at least one of them represents a radical CR 12 and that there cannot be more than 3 contiguous nitrogen atoms,
• Z 8 represents a nitrogen atom, a radical CR 15 ; • Re, R7, Rs, R9, R10. Ru, R1 2 , R 15 represent independently of each other
• CC o hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by one atom oxygen, nitrogen or sulfur or by an SO 2 group, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; the radicals R 6 to R 12 and R 15 not comprising a peroxide bond, nor of diazo or nitroso radicals and the radical Ru not being connected directly to the nitrogen atom by an oxygen, sulfur or nitrogen,
• the dye composition according to the present invention comprises, in a suitable medium, a compound of the following formula (I) or one of its addition salts:
• a linear or branched CrC 10 hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbon chain can be replaced by an atom d oxygen, nitrogen or sulfur or with an SO 2 group, and whose carbon atoms may be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino, (di) alkylamino radicals in
• R and R' 2 being as defined for R, and R 2
• R t and R 2 represent independently of each other: - a hydrogen atom
• halogen atom such as fluorine, chlorine, bromine
• a CC 4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, carboxy, alkoxycarbonyl radicals
• R ' 3 and R' 4 identical or different, represent a hydrogen atom; a CC 4 alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CC 4 alkoxy, amino, mono or di aikylamino, alkyl (CC 4 ) CO-, alkyl (CC 4 ) NHCO-, alkyl (CrC) radicals 4 ) SO 2 -,
• - n is an integer between 1 and 8
• - m is an integer between 0 and 3, preferably from 0 to 2
• - Y represents an oxygen atom, a radical CR ', a radical NR' 5 or a radical NR ' 6 R' 7 with R ' 5 which represents a hydrogen atom; a linear or branched C C ⁇ o hydrocarbon chain, which may be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group ) and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulfonic or thiol radicals; R ' 5 not comprising a peroxide bond, nor of diazo or nitroso radicals, and R' 5 not being directly connected to the nitrogen atom by an oxygen, sulfur or nitrogen atom, R ' 6 and R ' 7 which independently represent a linear or branched CC 10 hydrocarbon chain, which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which
• Z 2 , Z, Z 6 independently of one another represent a nitrogen atom, a radical CR 12 or NR-n with the proviso that at least one of them represents a radical CR 12 and that it cannot be more than 3 contiguous nitrogen atoms,
• Z 8 represents a nitrogen atom, a " CR 15 radical
• RQ, R 7 , R ⁇ , Rg, R 1 0, R 11 , Ri 2 , R 15 represent independently of each other - a hydrogen atom
• a linear or branched CC 10 hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an atom of oxygen, nitrogen or sulfur or with an SO 2 group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy, sulphonic or thiol; the radicals R ⁇ to R 12 and R 15 not comprising a peroxide bond, nor of diazo or nitroso radicals and the radical Ru not being connected directly to the nitrogen atom by an oxygen, sulfur or d atom 'nitrogen,
• the present invention also relates to a dye composition containing in a suitable medium at least one direct dye of the present invention.
• the composition of the present invention is particularly useful for dyeing keratin fibers, in particular human keratin fibers.
• the compounds of formula (I) are not only those described by formula (I) but any other tautomeric form such as for example the following tautomeric form:
• R 3 is preferably chosen from a hydrogen atom or a CC alkyl radical optionally substituted by one or more radicals chosen from hydroxy, CC 2 alkoxy, amino, (mono) - or (di) C- ⁇ -C 2 alkylamino, 2-hydroxyethyl, 2-aminoethyl.
• R 3 represents a hydrogen atom, a methyl, ethyl, 2-hydroxyethyl radical, even more preferable: a hydrogen atom or a methyl radical.
• the radicals R, and R 2 are preferably separately chosen from a hydrogen atom, an O ⁇ -C 6 alkyl radical optionally substituted by a hydroxy, alkoxy, amino, (mono) - or (di) alkylamino in CC 4 .
• R and R 2 are chosen from a hydrogen atom, a methyl, ethyl, hydroxyethyl, propyl, etc. radical.
• this heterocycle is preferably chosen from the heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine, diazepane optionally substituted.
• the heterocycle is chosen from the pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-NN- dimethylaminopyrrolidine, 3-acetamidopyrrolidine, 3- (methylsulfonylamino) - pyrrolidine, proline, 3-hydroxyproline, piperidine, hydroxypiperidine, ' homopiperidine, diazepane, N-methyl homopiperazine, N ⁇ -hydroxyethylhomopiperazine and their addition salts.
• Ri and R 2 form, with the nitrogen atom to which they are attached, an optionally substituted pyrrolidine ring.
• the compound of formula (I) is a cationic compound substituted with at least one onium Z radical, that is to say a cationic radical of the quaternary ammonium type.
• the onium radical Z can be represented by the following formula (III)
• • D is a covalent bond or a linear or branched C-rC alkylene chain which may contain one or more heteroatoms chosen from oxygen, sulfur or nitrogen, SO 2 , one or more ketone functions, the chain may be substituted by one or more hydroxyl, CC 6 alkoxy or amino, (mono) - or (di) alkylamino radicals CC; • R 16 , R 17 and R, 8, taken separately, represent a C 1 -C 15 alkyl radical; a CC 6 monohydroxyalkyl radical; a C 2 -C 6 polyhydroxyalkyl radical; alkoxy (CC 6) alkyl, CC 6; an aryl radical; a benzyl radical; a CC 6 amidoalkyl radical; a trialkyl radical (CC 6) alkylsilane C r C 6; a t -C 6 aminoalkyl radical; a CC 6 aminoalkyl radical in which the amine is mono- or di-substit
• R, 6 , R 17 and R, 8 together, two by two, form, with the nitrogen atom to which they are attached, a saturated carbonaceous cycle with 4, 5, 6 or 7 links which may contain one or more heteroatoms
• the cation cycle can be substituted by a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a CC 6 monohydroxyalkyl radical, a C 2 -C 6 polyhydroxyalkyl radical, a CC 6 alkoxy radical, a trialkyl (CrC 6) radical ) silanealkyle in C r C 6 , an amido radical, a carboxyl radical, a (C -C 6 ) carbonyl alkyl radical, a thio radical, a C ⁇ -C 6 thioalkyl radical, a thio (C ⁇ -C 6 ) alkyl radical , an amino radical, an amino radical mono- or di-substituted by an alkyl (CC 6 ),
• R 9 represents an alkyl radical in CrC 6 ; a C C 6 monohydroxyalkyl radical; a C 2 -C 6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a CC 6 aminoalkyl radical; a CC 6 aminoalkyl radical in which the amine is mono- or di-substituted by an alkyl radical (C 1 -C 6 ), alkyl (CrC 6 ) carbonyl, amido or alkyl (C 1 -C 6 ) sulfonyl; a C ⁇ -C 6 carboxyalkyl radical; a CC 6 carbamylalkyl radical; a CrC 6 trifluoroalkyl radical; a trialkyl (C ⁇ -C 6 ) silanealkyl radical in CC 6 ; a CC 6 sulfonamidoalkyl radical; a CC 6 carboxyalkyl (C ⁇ -C 6 ) alkyl radical; an al
• T is a counter ion.
• R z and R ⁇ 8 separately are preferably chosen from an alkyl radical in CC 6 , a monohydroxyalkyl radical in CrC 4 , a polyhydroxyalkyl radical in C 2 -C 4 , an alkoxy radical (CC 6 ) alkyl in C, -C, a amidoalkyl radical in C, -C 6 , a trialkyl radical (C, -
• R ⁇ 8 is then chosen from an alkyl radical in C ⁇ -C 6 ; a C r C 6 monohydroxyalkyl radical; a C 2 -C 6 polyhydroxyalkyl radical; a C ⁇ -C 6 aminoalkyl radical, an aminoalkyl radical in which the amine is mono- or disubstituted by an alkyl (CC 4 ), alkyl (CC 6 ) carbonyl, amido or alkyl (CC 6 ) sulfonyl radical; a CC 6 carbamylalkyl radical; a trialkyl radical (C ⁇ -C6) alkylsilane C ⁇ -C 6; a CC 6 carboxyalkyl (C r C 6 ) alkyl radical; an alkyl radical in C ⁇ -C 6 ; a C r C 6 monohydroxyalkyl radical; a C 2 -C 6 polyhydroxyalkyl radical; a C ⁇ -C 6 aminoalkyl radical, an aminoalkyl radical in which the amine is mono
• R, 9 is preferably chosen from a CC 6 alkyl radical; a monohydroxyalkyl radical in CrC 6 ; a C 2 -C 6 polyhydroxyalkyl radical; a C ⁇ -C 6 aminoalkyl radical, a CC 6 aminoalkyl radical in which the amine is mono or disubstituted by an alkyl (CrC 6 ), alkyl (O
• x is equal to 0 and R ⁇ 6 R ⁇ 7 and R 18 are alkyl radicals.
• D is preferably a covalent bond or a CC 6 alkylene chain which can be substituted.
• the onium radical Z can also be represented by the formula (IV)
• R which are identical or different, represent a hydrogen or halogen atom, a hydroxyl radical, an alkyl radical -C 6 monohydroxyalkyl radical -C 6 polyhydroxyalkyl radical a C 2 -C 6 alkoxy CC 6 , a trialkyl (CrC 6 ) silanealkyl radical in CrC 6 , an amido radical, a carboxyl radical, an alkylcarbonyl radical in CrC 6 , a thio radical, a thioalkyl radical in CrC 6 , an alkyl (CrCe) thio radical, a amino radical, an amino radical mono or di substituted by an alkyl (C ⁇ -C 6 ), alkyl (CrC 6 ) carbonyl, amido, alkyl (CrC 6 ) sulfonyl radical; monohydroxyalkyl radical -C 6 polyhydroxyalkyl radical or a C 2 -C 6; a benzyl radical; a pheny
• R 20 represents an alkyl radical in C Ce, a monohydroxyalkyl radical in CC 6 , a polyhydroxyalkyl radical in C 2 -C 6 , a trialkyl (CrC 6 ) silanealkyl radical in CrC 6 , an alkoxy radical (G
• the link arm D is attached to one of the vertices E, G, J or L when E, G, J or L. represent a carbon atom
• T is a counterion.
• the vertices E, G, J and L form an imidazolic, pyrazolic, oxazolic, thiazolic and triazolic cycle.
• x is equal to 0 and D is a covalent bond or a CC 4 alkylene chain which can be substituted.
• the onium radical Z can be represented by the formula (V) ( R 1S)) ⁇ _
• the vertices E, G, J, L and M which are identical or different, represent a carbon or nitrogen atom and form a cycle chosen from the pyridine, pyrimidine, pyrazine, triazine and pyridine cycles,
• T represents a counter ion
• the vertices E, G, J, L and M with the nitrogen of the cycle form a cycle chosen from the pyridine, pyrimidine, pyridine and pyrazine cycles.
• x is 0 and R is chosen from a hydroxyl radical, an alkyl radical -C 6 monohydroxyalkyl radical -C 6 polyhydroxyalkyl radical a C 2 -C 6 radical alkoxy -C 6 trialkyl radical (Cr C 6) alkylsilane -C 6, an amido radical, an alkylcarbonyl C r C 6 radical, an amino radical, an amino radical mono- or di-substituted by alkyl (Ci-C 6 ), alkyl (C ⁇ -C 6 ) carbonyl, amido or alkyl (CrC 6 ) sulfonyl; monohydroxyalkyl radical -C 6 polyhydroxyalkyl radical or a C 2 -C 6; it being understood that the radicals R are carried by a carbon atom.
• x is equal to 1
• R 19 is chosen from a CC 6 alkyl radical; a CC 6 monohydroxyalkyl radical; a C 2 -C 6 polyhydroxyalkyl radical; an aminoalkyl radical -C 6 aminoalkyl radical in C r C 6 whose amine is mono- or disubstituted by a radical a!
• Rig is an alkyl radical in O, -0, which can be substituted and R, a hydrogen atom, an alkyl radical in CC 4 which can be substituted.
• the compound of formula (I) is a cationic compound substituted by a radical Z, preferably at least one of the radicals Ri and R 2 represents an onium radical Z.
• Ri and R 2 form a ring of formula (II) in which R 'is an onium radical Z, preferably with Y equal to NR' 6 R ' 7 .
• W1 represents in particular the 5-aminopyrazole,, 5-hydroxypyrazole, pyrazolo- [1, 5-b] -pyridine, pyrazolp- [1 , 5-a] - pyrimidine, pyrazolo radicals [3 , 2-c]. triazole, pyrazp, lo [1., 5-p] trjazole, aminopyrimidines, triaminopyrimidine, hydroxyaminopyrimidines, 2-aminopyridine, indoline and indole. •
• VV1 is chosen from 5-aminopyrazole, 5-hydroxypyrazole radicals. of formula (R1).
• W1 is chosen from. preferably from the 5-aminopyrazole and 5-hydroxypyrazoIe radicals in which R6 and R1.1, which are identical or different, are chosen from one. hydrogen atom,;. a hydrocarbon chain; in linear or branched form, which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by, an oxygen atom , nitrogen or sulfur or by a grouping sp.
• the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy radicals. amino, carboxy, sulfonic or thiol; the radicals R 6 to R 12 not comprising Ijajson. peroxide, nor of .diazo or nitroso radicals and the radical R11, not being. not. linked directly to the atom , nitrogen by an oxygen, sulfur or nitrogen atom. ,
• R1, R6 and R11 are independently chosen from a hydrogen atom or a linear or branched CrC 4 hydrocarbon chain, can form one or more carbon rings comprising from .5 to 6 members , and can be saturated or unsaturated, the carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino radicals.
• W1 represents
• R6, R7, R8, R9 and Z8 being such that ns pr c emmen.
• W1 can be a pyrazolo- [1, 5-b] - pyridine radical in which R 6 , R 7 , R 8 , R 9 and R 15 , identical or different, are chosen from
• a linear or branched C -C 0 hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which may be replaced by a oxygen, nitrogen or sulfur atom or by an SO 2 group, and the carbon atoms of which may be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, carboxy radicals, sulfonic or thiol; radicals not comprising a peroxide bond, nor of diazo or nitroso radicals,
• the amine can be substituted by a linear or branched CC 4 hydrocarbon chain, which can form one or more carbon rings comprising from 5 to 6 members, and which can be saturated or unsaturated, carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino radicals.
• W1 can also be a pyrazolo- [1, 5-b] - pyridine radical in which R_, R 7 , R 8 , R g and R 5 , identical or different, are chosen from
• a linear or branched CrC ⁇ 0 hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 links, and which can be saturated or unsaturated, one or more carbon atoms of the carbon chain of which can be replaced by an atom d oxygen, nitrogen or sulfur or by an SO 2 group, and whose carbon atoms may be, independently of each other, substituted by one or more atoms halogen or hydroxy, amino, carboxy, sulfonic or thiol radicals; radicals not comprising a peroxide bond, nor of diazo or nitroso radicals,
• W1 can also be a pyrazolo- [1, 5-b] - pyridine radical in which Re, R 7 , Rg, R 9 and R 15 , identical or different, are chosen from
• a linear or branched C1-C 10 hydrocarbon chain which can form one or more carbon rings comprising from 4 to 8 members, and which can be saturated or unsaturated, and whose carbon atoms can be, independently of one another, substituted by one or more halogen atoms or hydroxy, amino, mono or disubstituted amino, C1-C4 alkoxy, C1-C4 thioether, carboxy, sulfonic or thiol;
• the amine can be substituted by a linear or branched CC 4 hydrocarbon chain, which can form one or more - carbon rings comprising from 5 to 6 members, and which can be saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino radicals.
• W1 is a pyrazolo- [1,5-b] -pyridine radical
• the radicals Re, R 7 , R 8 , R 9 and R 15 are preferably chosen from a hydrogen atom, a linear CC hydrocarbon chain or branched and possibly saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy or amino radicals.
• W1 can also be a pyrazolo- [1,5-a] -pyrimidine radical in which R7 and R9 are chosen from a hydrogen atom, a linear or branched C r C 6 alkyl radical; a CC 6 monohydroxyalkyl radical; a C 2 -C 6 polyhydroxyalkyl radical; an aminoalkyl radical -C 6 aminoalkyl -C 6 whose amine is mono- or di- substituted with an alkyl radical (C r -C 6) alkyl (Ci-C 6) alkoxycarbonyl; a hydroxy or amino radical, the amino being able to be substituted by a linear or branched C C ⁇ o hydrocarbon chain, being able to form one or more carbon rings having 5 to 6 members, and being able to be saturated or unsaturated, the carbon atoms can be, independently of each other, substituted by one or more halogen atoms or hydroxy, amino radicals; R6 and R8 are chosen from a hydrogen atom
• R7 and R9 are preferably chosen from a hydrogen atom; a linear or branched CC 4 alkyl radical; a CC monohydroxyalkyl radical; a C 2 -C 4 polyhydroxyalkyl radical; an aminoalkyl radical -C 4 aminoalkyl DC 4 whose amine is mono- or di- substituted with an alkyl (Ci-C 2); a hydroxy or amino radical, the amino being able to be substituted by a linear or branched CrC hydrocarbon chain, the carbon atoms can be, independently of one another, substituted by one or more hydroxy, amino, and R6 and R8 radicals are preferably chosen from a hydrogen atom, a linear or branched CC 4 alkyl radical; a CC monohydroxyalkyl radical; a C 2 -C polyhydroxyalkyl radical; an aminoalkyl radical -C 4 aminoalkyl radical whose amine CC 4 is mono- or di- substituted with an alkyl (Ci-C
• W1 is a pyrazolopyridine or pyrazolopyrimidine derivative in which R6, R7, R8 and R9 are preferably chosen from a hydrogen atom; a C1-C4 alkyl radical; an amino radical; a mono or di C1-C4 alkylamino radical; a C1-C4 hydroxyalkyl radical; a G, -C 2 alkoxy radical.
• R6, R7, R8 and R9 are preferably chosen from a hydrogen atom; a C1-C4 alkyl radical; an amino radical; a mono or di C1-C4 alkylamino radical; a C1-C4 hydroxyalkyl radical; a G, -C 2 alkoxy radical.
• R6, R7, R8 and R9 are preferably chosen from a hydrogen atom; a C1-C4 alkyl radical; an amino radical; a mono or di C1-C4 alkylamino radical; a C1-C4 hydroxyalky
• R1, R2, R6 are as defined above.
• the composition of the invention preferably contains an amount of compound of formula (I) of between 0.01 and 10% by weight, preferably from 0.1 to 5%.
• the dye composition in accordance with the invention may also contain direct dyes different from the compounds of formula (I). These direct dyes which are useful according to the invention are, for example, chosen from neutral, acidic or cationic benzene nitro direct dyes, neutral azo acidic or cationic direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes azines, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
• benzene direct dyes the following compounds may be mentioned without limitation: -1, 4-diamino-2-nitrobenzene
• azo direct dyes mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention.
• triarylmethane dyes mention may be made of the following compounds: -Basic Green 1
• the direct dye (s) preferably represent from 0.001 to 20% by weight approximately of the total weight of the ready-to-use composition and even more preferably from 0.005 to 10% by weight approximately.
• composition of the present invention may also contain oxidation bases and couplers conventionally used for coloring by oxidation.
• para-phenylenediamines bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.
• the couplers are, for example, meta-phenylenediamine couplers, meta-aminophenol couplers, meta-diphenol couplers, naphthalene couplers, heterocyclic couplers and their addition salts.
• the bases and the couplers are each generally present in an amount of between 0.001 and 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.
• the medium suitable for dyeing also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water.
• organic solvent mention may, for example, be made of lower C 1 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
• lower C 1 alkanols such as ethanol and isopropanol
• polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
• the dyeing medium is an appropriate cosmetic medium.
• the solvents may be 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 dye composition in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers , cationic, non-ionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative thickeners anionic, cationic, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
• adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers , cationic, non-ionic, amphoteric, zwit
• These adjuvants above 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 dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately.
• the acidifying agents there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
• the basifying agents there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of the following formula (III):
• the dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
• the invention also relates to a direct dyeing process which comprises the application of a dye composition containing a dye of formula (I) as defined above on keratin fibers. After a pause, the keratin fibers are rinsed leaving colored fibers to appear.
• the pause time is generally between 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately.
• the dye composition may then contain an oxidizing agent.
• the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes among which there may be mentioned peroxidases, oxidoreductases with 2 electrons such as uricases and oxygenases with 4 electrons such as laccases. Hydrogen peroxide is particularly preferred.
• the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it, applied simultaneously or sequentially to the composition of the invention.
• the oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
• the pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.
• composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.
• oxidation base is intended to mean the heterocyclic oxidation bases conventionally used in coloring which, after reaction with the coupler formed, a radical W1.
• the coupler used is a 2,3 diaminopyridine coupler substituted in position 6 by a leaving group such as an alkoxy, a halogen atom, an aryloxy, - OSO 2 R, a radical -OCOR, a trifluoroalkoxy radical in CC 3 , with R representing an alkyl radical.
• the base and the coupler are mixed with a solvent, for example acetonitrile.
• a base for example, sodium hydroxide and CAN, is added to this mixture.
• water is added to the reaction medium.
• the aqueous phase is extracted for example with ethyl acetate.
• the organic phase is eliminated.
• the aqueous phase is again extracted, for example with butanol.
• the butanolic phase is subsequently dried, filtered and then concentrated, then purified.
• 3-amino-7-diethylaminopyrazolopyrimidine (A: 0.440 g), 2-pyrrolidino-3-amino-6-methoxypyridine (B: 0.386 g), ethanol / water ((60/40), 40 g), H2O2 ( 20 vol, 50 g) and a buffer at pH 7 (10 g of buffer: H2KPO4 13.6 g; HK2PO426.1g and Water qs 100 ml) are mixed and stirred at room temperature for 1 hour. The reaction mixture is then precipitated and the dye obtained (C) is purified by column chromatography.
• 0.238 g of A (0.45 mmol; 2 eq.) And 0.050 g of B (0.22 mmol; 1 eq.) are introduced into 10 ml of acetonitrile. 338 mg of 35% sodium hydroxide diluted in 10 ml of water are then added, then 499 mg of CAN immediately. The solution takes a gray tint in a few minutes. After 4 hours of stirring, 100 ml of water are added. The aqueous phase is extracted with ethyl acetate. The organic phase is eliminated. The aqueous phase is again extracted with butanol. The butanolic phase is subsequently dried over sodium sulfate, filtered and then concentrated. The product is taken up in ethanol (2 ml) and then precipitated again in diisopropyl ether. A black powder is obtained (C).

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