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WO2007071684A2 - Composition for dyeing keratin fibres with a tetraazapentamethine cationic direct dye and an amino silicone - Google Patents

Composition for dyeing keratin fibres with a tetraazapentamethine cationic direct dye and an amino silicone Download PDF

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Publication number
WO2007071684A2
WO2007071684A2 PCT/EP2006/069928 EP2006069928W WO2007071684A2 WO 2007071684 A2 WO2007071684 A2 WO 2007071684A2 EP 2006069928 W EP2006069928 W EP 2006069928W WO 2007071684 A2 WO2007071684 A2 WO 2007071684A2
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Prior art keywords
formazano
chloride
pyridinylidene
radical
methyl
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French (fr)
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WO2007071684A3 (en
Inventor
Marie-Pascale Audousset
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LOreal SA
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LOreal SA
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Priority claimed from FR0554058A external-priority patent/FR2895242B1/en
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    • 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
    • A61K8/4906—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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • 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 invention relates to a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising, in a suitable dyeing medium, at least one tetraazapentamethine cationic direct dye, and which is characterized in that it also contains at least one amino silicone.
  • the invention also relates to the processes and dyeing devices using the said composition.
  • Two types of dyeing may be distinguished in the field of hair dyeing.
  • the first is semi-permanent or temporary dyeing, or direct dyeing, which involves dyes capable of giving the hair's natural coloration a more or less pronounced colour change, which may be resistant to shampoo washing several times.
  • These dyes are known as direct dyes; they may be used with or without an oxidizing agent.
  • the aim is to obtain lightening dyeing.
  • Lightening dyeing is performed by applying to the hair an extemporaneous mixture of a direct dye and an oxidizing agent, and makes it possible especially to obtain, via lightening of the melanin of the hair, an advantageous effect such as a unified colour in the case of grey hair, or to bring out the colour in the case of naturally pigmented hair.
  • the second is permanent dyeing or oxidation dyeing.
  • oxidation dyes comprising oxidation dye precursors and couplers.
  • Oxidation dye precursors commonly known as “oxidation bases” are compounds that are initially colourless or weakly coloured, which develop their dyeing power on the hair in the presence of oxidizing agents added at the time of use, leading to the formation of coloured compounds and dyes.
  • the formation of these coloured compounds and dyes results either from an oxidative condensation of the "oxidation bases” with themselves, or from an oxidative condensation of the "oxidation bases” with coloration modifiers commonly known as “couplers", which are generally present in the dye compositions used in oxidation dyeing.
  • direct dyes may be added thereto.
  • a first subject of the present invention is thus a composition for dyeing keratin fibres and in particular human keratin fibres such as the hair, containing, in a suitable dyeing medium, (i) at least one cationic direct dye whose structure corresponds to formula (I) defined below, characterized in that it also contains (ii) at least one amino silicone:
  • W 1 represents a cationic heteroaromatic radical of formula (II) or (III):
  • W 2 represents a heteroaromatic radical of formula (IV) or (V):
  • Z 0 represents a radical CR 2 , a nitrogen atom or a radical NR 21
  • Z 1 represents an oxygen or sulfur atom or a radical NR 9
  • Z 2 represents a nitrogen atom or a radical CR 10 ,
  • Z 3 represents a nitrogen atom or a radical CRn
  • Z 4 represents a nitrogen atom or a radical CR 12
  • - Z 5 represents a nitrogen atom or a radical CR 13
  • Z 6 represents a nitrogen atom or a radical CR 14 ,
  • Z 7 represents an oxygen or sulfur atom or a radical NR 15 ,
  • Z 8 represents a nitrogen atom or a radical CR 16 ,
  • Z 9 represents a nitrogen atom or a radical CR 17
  • - Z 10 represents a nitrogen atom or a radical CR 18
  • Z 11 represents a nitrogen atom or a radical CR 19 ,
  • Z 12 represents a nitrogen atom or a radical CR 20 ,
  • Z 13 represents a radical CR 6 , a nitrogen atom or a radical NR 22 , it being understood that each of the rings of formulae (II), (III), (IV) and (V) comprise not more than three nitrogen atoms and that two of the three nitrogen atoms may be contiguous, the bond a of the 5-membered cationic heteroaromatic radical of formula (II) being linked to the nitrogen atom N 1 of formula (I), the bond b of the 6-membered cationic heteroaromatic radical of formula (III) being linked to the nitrogen atom N 1 of formula (I), the double bond a' of the 5-membered heteroaromatic radical of formula (IV) being linked to the nitrogen atom N 2 of formula (I), the double bond b' of the 6-membered heteroaromatic radical of formula (V) being linked to the nitrogen atom N 2 of formula (I), - the bond b, linking the cationic heteroaromatic radical of formula (III) to the nitrogen atom N 1 of formula (
  • (di)alkylamino, carboxyl and sulfonic radicals a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, amino and CrC 2 (di)alkylamino radicals; a carboxyl radical; a sulfonylamino radical,
  • Ri, R 4 , R 5 , R 7 , Rg, Ri 5 , R 21 and R 22 represent, independently of each other, a linear or branched C 1 -C 8 alkyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, amino, C 1 -C 2 (di)alkylamino, carboxyl and sulfonic radicals;
  • Ri9 and R 2 o represent, independently of each other, a hydrogen atom, a linear or branched C 1 -C 16 hydrocarbon-based chain, this chain possibly being saturated or unsaturated with one to three unsaturations, this chain being unsubstituted or substituted with one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, amino, C 1 -C 2 (di)alkylamino, carboxyl, sulfonic, sulfonylamino and C 2 -C 4 (poly)hydroxyalkylamino radicals or a halogen atom such as chlorine, fluorine or bromine; a phenyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly)
  • R 2 with R 10 , R 1 - I with R 12 , R 6 with R 16 , and R 17 with R 18 can form, independently of each other, a 5- or 6-membered carbon-based aromatic ring, which is unsubstituted or substituted with one or two hydroxyl, amino, (di)(C 1 -C 2 )alkylamino, C 1 -C 2 alkoxy or C 2 -C 4 (poly)hydroxyalkylamino radicals, X is an organic or mineral anion.
  • branched hydrocarbon- based chain means a branched hydrocarbon-based chain that may also form one to five 3- to 7-membered carbon-based rings, this chain possibly comprising one to three unsaturations, i.e. one to three double bonds and/or triple bonds.
  • C 2 -C 4 (poly)hydroxyalkoxy means a C 2 -C 4 alkoxy group substituted with 1 or 2 hydroxyl groups.
  • C 2 -C 4 (poly)hydroxyalkylamino means an alkylamino group substituted with 1 or 2 hydroxyl groups.
  • hydrocarbon-based chain may be interrupted with one or more oxygen, nitrogen or sulfur atoms or with an SO 2 radical, or according to which this chain is unsaturated, means that the carbon-based chain may be modified in the following manner:
  • J-CHr-CH 3 can become [-O-CH
  • an organic or mineral anion is chosen, for example, from a halide such as chloride, bromide, fluoride or iodide; a hydroxide; a sulfate; a hydrogen sulfate; a (d-C 6 )alkyl sulfate, for instance a methyl sulfate or an ethyl sulfate; an acetate; a tartrate; an oxalate; a (Ci-C 6 )alkylsulfonate such as methyl sulfonate; an aryisulfonate, which is unsubstituted or substituted with a C 1 -C 4 alkyi radical, for instance a 4- tolylsulfonate.
  • a halide such as chloride, bromide, fluoride or iodide
  • a hydroxide such as chloride, bromide, fluoride or iodide
  • a hydroxide such
  • R 0 represents a hydrogen atom; a linear or branched Ci-C 6 alkyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, CrC 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, amino, C 1 -C 2 (di)alkylamino, C 2 -C 4 (poly)hydroxyalkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, Ci-C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, amino, Ci-C 2 (di)aikylamino, carboxyl and sulfonic radicals or a halogen atom such as chlorine, fluorine or bromine, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thi
  • R 0 preferably represents a hydrogen atom; a linear or branched Ci-C 3 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, amino, Ci-C 2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, C 1 -C 2 (di)alkylamino and C 2 -C4 (poly)hydroxyalkylamino radicals, or an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl and pyridyl radicals.
  • R 0 represents a hydrogen atom; a methyl, ethyl, propyl, butyl, 2-hydroxyethyl, 2-aminoethyl, 1-carboxy methyl, 2-carboxyethyl, 2-sulfonylethyl or 2-methoxyethyl; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from amino, Ci-C 2 (di)alkylamino and C 2 -C 4 (poly)hydroxyalkylamino radicals, or an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl and pyridyl radicals.
  • R 0 even more preferably represents a hydrogen atom; a methyl, ethyl or 2-methoxyethyl radical; a phenyl radical, which is unsubstituted or substituted with an amino, (di)methylamino or (di)(2-hydroxyethyl)amino radical, or an optionally cationic heteroaryl radical chosen from imidazolyl and pyridyl radicals.
  • R 2 , R 6 , R 10 and Ri 6 preferably represent a hydrogen atom, a phenyl radical or a CrC 4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, CrC 2 (di)alkylamino and carboxyl radicals.
  • R 2 , R 6 , R 10 and Ri 6 preferably represent a hydrogen atom, a methyl, phenyl or 2-hydroxymethyl radical, a carboxyl or a phenyl radical.
  • R 1 , R 4 , R 5 , R 7 , R 9 , Ri 5 , R 2i and R 22 preferably represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl or 2- sulfonylethyl radical.
  • R 3 , R 8 , R 11 , R 12 , R 13 , R 14 , Ri 7 , R 18 , R 19 and R 20 preferably represent, independently of each other, a hydrogen atom; a linear or branched Ci-C 4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, amino, Ci-C 2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, Ci-C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, amino, C 1 -C 2 (di)alkylamino, carboxyl and sulfonic radicals or a halogen atom such as chlorine, fluorine or bromine; a sulfony
  • R 3 , R 8 , Rn, R 12 , R13, Ru, R17, Ri ⁇ > R19 and R 2 o represent a hydrogen atom, a C 1 -C 4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl radicals or a C 1 -C 2 alkoxy radical; an amino radical; a C 1 -C 2 (di)alkylamino radical; a carboxyl radical; a C 2 -C 4 (poly)hydroxyalkylamino radical.
  • R 3 , R 8 , R- ⁇ , R 12 , R 13 , R 14 , R 17 , R 18 , Ri 9 and R 20 represent, independently of each other, a hydrogen atom, a methyl or 2- hydroxymethyl radical, a carboxyl, a methoxy, ethoxy or 2-hydroxyethyloxy radical, or an amino, methylamino, dimethylamino or 2-hydroxyethylamino radical.
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-pyridinium radical and W 2 is a 2-pyridine radical. Even more preferably, they are the following compounds:
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 4-pyridinium radical and W 2 is a 4-pyridine radical. Even more preferably, they are the following compounds: - 4-[5-(N-methyl-4-pyridinylidene)-1-formazano]-N-methylpyridinium chloride
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-imidazolium radical and W 2 is a 2-imidazole radical. Even more preferably, they are the following compounds:
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 5-pyrazolium radical and W 2 is a 5-pyrazole radical. Even more preferably, they are the following compounds: - 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-1-formazano]-1 ,2-dimethylpyrazolinium chloride
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-benzimidazolium radical and W 2 is a 2- pyridine radical. Even more preferably, they are the following compounds:
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-benzimidazolium radical and W 2 is a A- pyridine radical. Even more preferably, they are the following compounds:
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-imidazolium radical and W 2 is a 2-pyridine radical. Even more preferably, they are the following compounds: - 2-[5-(N-methyl-2-pyridinylidene)-1-formazano]-1 ,3-dimethylimidazolium chloride
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-imidazolium radical and W 2 is a 4-pyridine radical. Even more preferably, they are the following compounds: - 2-[5-(N-methyl-4-pyridinylidene)-1-formazano]-1 ,3-dimethylimidazolium chloride
  • the compounds of formula I are chosen from the family defined by the compounds for which W 1 is a 2-benzimidazolium radical and W 2 is a 2-benzimidazole radical. Even more preferably, they are the following compounds:
  • the compounds of family A (first variant) will be preferred most particularly.
  • the compound(s) of formula (I) is (are) preferably present in a concentration ranging from 0.001% to 10%, preferably from 0.005% to 5% and even more preferentially from 0.01% to 2% by weight relative to the total weight of the composition.
  • the compounds of formula (I) may especially be obtained via a process in which at least two equivalents of at least one hydrazone chosen from the hydrazones of formula A and the hydrazones of formula B:
  • Z 14 , Z 15 , Z 16 and R25 have the same meanings as Z 7 , Z 8 , Z 13 , and R 5 , respectively, of formula IV,
  • Y being an organic or mineral anion
  • x being an integer ranging from 1 to 3
  • Z 17 , Z 18 , Z 19 , Z 20 , R26 and R 27 have the same meanings as Z 9 , Z 10 , Z 11 , Z 12 , R 8 and R 7 , respectively, of formula V,
  • Y' being an organic or mineral anion, x' being an integer ranging from 1 to 3, are reacted with one equivalent of an aldehyde of formula R 23 CHO, R 23 having the same meaning as Ro of formula I. Two equivalents of the same hydrazone or of two different hydrazones may thus be reacted.
  • the aldehyde of formula R 23 CHO is generated in the reaction medium from an aldehyde precursor of formula R' 23 CH 2 OH in the presence of an oxidizing system; R' 23 then has the same meaning as R 0 of formula I.
  • This oxidizing system may be a chemical oxidizing agent or a biocatalytic oxidizing agent such as an enzyme.
  • the process for preparing the compound of formula (I) according to the present invention may be performed in the presence of an aldehyde precursor of formula R' 23 CH 2 OH and of at least one enzyme capable of generating an aldehyde from the aldehyde precursor of formula R' 23 CH 2 OH.
  • the process for enzymatically synthesizing the compounds of formula (I) defined above is performed by reacting at least two equivalents of at least one hydrazone chosen from the hydrazones of formula A and the hydrazones of formula B in which Z 14 , Z 15 , Zi 6 and R 25 have the same meanings as Z 7 , Z 8 , Zi 3 and R 5 , respectively, of formula IV,
  • Y being an organic or mineral anion
  • x being an integer ranging from 1 to 3
  • Z 17 , Z 18 , Z 19 , Z 20 , R26 and R 27 having the same meanings as Z 9 , Zi 0 , Z 11 , Z 12 , R 8 and R 7 , respectively, of formula V, Y' being an organic or mineral anion, x' being an integer ranging from 1 to 3, with one equivalent of an aldehyde of formula R 23 CHO, R 23 having the same meaning as R 0 of formula I.
  • the reaction is performed with or without an oxidizing system, with or without a cofactor for the enzyme, and with or without a system for regenerating the cofactor.
  • the term "without an oxidizing system” means that no oxidizing system other than atmospheric oxygen is used.
  • the reaction is performed in aerobic medium at a pH of between 3 and 11 and at a temperature of between 6 0 C and 8O 0 C.
  • the aldehyde precursor that may be used to prepare the compound of formula (I) may be chosen from primary alcohols, sarcosine, 4-hydroxymandelate, N6- methyllysine, dimethylglycine, methylglutamate, 2-oxo acids, for example 2-oxo acid pyruvate, benzoylformate, phenyl pyruvate or threonine. It will preferably be chosen from primary alcohols.
  • the enzymes capable of generating an aldehyde from this aldehyde precursor may be chosen especially from the alcohol dehydrogenases EC 1.1.1.1, the alcohol dehydrogenases EC 1.1.1.2, the alcohol dehydrogenases EC 1.1.1.71 , the aromatic alcohol dehydrogenases EC 1.1.1.90, also known as aryl alcohol dehydrogenases, the aromatic alcohol dehydrogenases EC 1.1.1.97, the 3-hydroxybenzyl alcohol dehydrogenases EC 1.1.1.97, the coniferyl alcohol dehydrogenases EC 1.1.1.194, the cinnamyl alcohol dehydrogenases EC 1.1.1.195, the methanol dehydrogenases EC 1.1.1.244, the aromatic alcohol oxidases EC 1.1.3.7, also known as aryl alcohol oxidases, the alcohol oxidases EC 1.1.3.13, the A- hydroxymandelate oxidases EC 1.1.3.19, the long-chain hydrocarbon alcohol oxid
  • N-methyl L-amino acid oxidase EC 1.5.3.2 N-methyl-L-amino acid
  • trimethylamine dehydrogenase EC 1.5.99.7 trimethylamine
  • dimethylamine dehydrogenase EC 1.5.99.10 dimethylamine
  • nitroethane oxidase EC 1.7.3.1 nitrogenethane
  • acetoin ribose 5 phosphate transaldolase EC 2.2.1.4 (3-hydroxybutan-2-one), diamine aminotransferase EC 2.6.1.29 (alpha omega diamine + 2- oxogluterate), alkenylglycerophosphocholine hydrolase EC 3.3
  • alkenylglycerophosphocholine alkenylglycerophosphoethanolamine hydrolase EC 3.3.2.5 (alkenylglycerophosphocholine), alkylalidase EC 3.8.1.1 (halomethane), phosphonoacetaldehyde hydrolase EC 3.11.1.1 (phosphonoacetaldehyde), indolepyruvate decarboxylase EC 4.1.1.74 (3-indol-3-yl pyruvate) mandelonitrile lyase EC 4.1.2.10 (mandelonitrile), hydroxymandelonitrile lyase EC 4.1.2.11 (hydroxymandelonitrile), ketopantoaldolase EC 4.1.2.12 (2-hydroxy-2-isopropylbutanedioate), dimethylaniline-N-oxide aldolase EC 4.1.2.24 (dimethylaniline-N-oxide), phenylserine aldolase EC 4.
  • the enzyme capable of generating an aldehyde from the aldehyde precursor used in the dye composition according to the invention may be derived from an extract of plants, of animals, of microorganisms (bacterium, fungus, yeast or microalga) or from viruses, or from cells that are differentiated or undifferentiated, obtained in vivo or in vitro, which are genetically modified or unmodified, or synthetic (obtained via chemical or biotechnological synthesis).
  • Examples of useful enzymes that may be mentioned in particular are the genera Plectranthus, Pinus, Gastropode, Manduca, Pichia, Candida, Pleurotus, and Pseudomonas, and even more particularly the following species: Plectranthus colloides, Pinus strobus, which is a species of plant origin, Gastropode mollusc and Manduca sexta, which are of animal origin, Pichia pastoris and Candida boidinii, which are yeasts, Pleurotus pulmonarius, which is a fungus, and Pseudomonas pseudoalcaligenes, which is a bacterium.
  • Plectranthus colloides Pinus strobus, which is a species of plant origin
  • Gastropode mollusc and Manduca sexta which are of animal origin
  • Pichia pastoris and Candida boidinii which are yeasts
  • Pleurotus pulmonarius which is a fungus
  • the choice of the enzyme depends on the nature of the aldehyde precursor. For example, when the aldehyde precursor is an alcohol, then the enzyme is chosen from enzymes capable of generating an aldehyde from this alcohol. When the aldehyde precursor is methylglutamate, then the enzyme is a methylglutamate dehydrogenase.
  • the aldehyde precursor is a primary alcohol and the enzyme is an enzyme capable of generating the aldehyde from an alcohol.
  • the enzyme capable of generating the aldehyde is chosen from alcohol oxidases, alcohol dehydrogenases, methanol dehydrogenases and methanol oxidases.
  • the primary alcohol is benzyl alcohol, 4-tert- butylbenzyl alcohol, 3-hydroxy-4-methoxybenzyl alcohol, veratryl alcohol, 4-methoxybenzyl alcohol, cinnamyl alcohol or 2,4-hexadien-1-ol, aryl alcohol oxidases or aromatic alcohol dehydrogenases may be used as aldehyde precursor.
  • the enzyme dehydrogenases it is essential to include the cofactor(s) required for their activity, more specifically NAD + or NADP + or other molecules capable of acting as electron acceptor.
  • the addition of a system for regenerating the cofactors may be used for reaction purposes or economic purposes. This regeneration system may be enzymatic, chemical or electrochemical.
  • oxidizing agents may be used to perform this process: aqueous hydrogen peroxide solution, organic peracids such as peracetic acid, persalts such as permanganate, perborate and persulfates, chromates or dichromates, hypochlorites, hypobromites, ferricyanides, and peroxides such as manganese dioxide or lead dioxide.
  • Aqueous hydrogen peroxide solution will preferably be used.
  • the concentration of enzyme substrate may be between 0.001 M and 6 M and preferably between 0.1 M and 4 M.
  • the reaction may be performed between pH 3 and pH 11 and preferably between pH 5 and pH 9.5.
  • the reaction temperature may be between 10 0 C and 80 0 C and preferably between 20 0 C and 65°C.
  • the hydrazone concentration of the reaction medium is between 0.01 M and 3 M and preferably between 0.1 M and 1 M.
  • the content of cofactor for said enzymes may be between 0.01 mM and 1 M and preferably between 0.1 mM and 10 mM.
  • the reagents the hydrazone(s), the enzyme(s), the substrate for said enzyme, and/or the cofactor for said enzyme, and the oxidizing agent and/or the system for regenerating the cofactor are mixed together, and the pH and the temperature are adjusted.
  • the compounds of formula I may also be prepared via a process in which a compound of formula (F1) or (F2)
  • Formula Fl Formula F2 with Z 14 , Z 15 , Z 16 , Ro, R24 and R25 for formula F1 and Z 17 , Z 18 , Z 19 , Z 20 , Ro, R24 and R 26 for formula F2 having the meanings described above, is reacted in the presence of one equivalent of a hydrazone of formula (A) or (B).
  • the compounds of formula (F1 ) or (F2) may be obtained by reacting a compound of formula R"23C(OR 24 ) 3 and a hydrazone of formula (A) or (B) in the presence or absence of a protic solvent whose boiling point ranges between 66 0 C and 180 0 C.
  • R" 23 has the same meaning as R 0 of formula (I) and R 24 represents a radical chosen from methyl and ethyl groups.
  • the reaction is performed in the presence of triethyl orthoformate and trimethyl orthoacetate at a temperature of between 0°C and 150 0 C for a period of between 30 minutes and 12 hours.
  • the protic solvent is chosen from H 2 O, ethanol and methanol.
  • amino silicone means any silicone comprising at least one primary, secondary or tertiary amine or a quaternary ammonium group.
  • the amino silicones may be in the form of oils or of aqueous, alcoholic or aqueous-alcoholic solutions.
  • the amino silicones may also be in the form of oil-in-water emulsions.
  • the oil-in-water emulsion may comprise one or more surfactants.
  • the surfactants may be of any nature but are preferably cationic and/or nonionic.
  • the number-average size of the silicone particles in the emulsion is generally between 3 nm and 500 nm, preferably between 5 nm and 300 nm, more particularly between 10 nm and 275 nm and even more preferentially between 150 and 275 nm.
  • amino silicones may be chosen especially from the following compounds: (a) amino silicones corresponding to the formula:
  • G is a hydrogen atom or a phenyl, OH or Ci-C 8 alkyl, for example methyl, group, a denotes the number 0 or an integer from 1 to 3, in particular 0, b denotes 0 or 1 , and in particular 1 , m and n are numbers such that the sum (n + m) can range especially from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and in particular from 49 to 149 and m possibly denoting a number from 1 to 2000, and in particular from 1 to 10; R' is a monovalent radical of formula -C q H 2q L in which q is a number from 2 to 8 and
  • L is an optionally quaternized amine group chosen from the groups: -NR"-CH 2 -CH 2 -N'(R") 2 -N(R") 2 -N ⁇ (R") 3 A- -NH ® (R") 2 A-
  • R" can denote hydrogen, phenyl, benzyl or a saturated monovalent hydrocarbon- based radical, for example an alkyl radical containing from 1 to 20 carbon atoms, and A " represents a halide ion such as, for example, fluoride, chloride, bromide or iodide.
  • n' + n" is equal to n+1 , n and m corresponding to the definitions given for the compounds of formula (Vl). It is thus possible to use, for example, the product sold under the name "Cationic Emulsion DC 939" by the company Dow Corning, which comprises, besides amodimethicone, a cationic surfactant trimethylcetylammonium chloride in combination with a nonionic surfactant Trideceth-12.
  • n and m have the meanings given for formula (Vl).
  • n and n are numbers such that the sum (n + m) may range especially from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and especially from 49 to 149, and m possibly denoting a number from 1 to 2000 and especially from 1 to 10;
  • A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.
  • the weight-average molecular mass of the amino silicones preferably ranges from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.
  • the viscosity at 25 0 C of the amino silicone is especially greater than 25 000 cSt (mm 2 /s) and preferably ranges from 30 000 to 200 000 cSt (mm 2 /s) and more particularly from 30 000 to 150 000 cSt (mm 2 /s).
  • These amino silicones preferably have an amine number of less than or equal to 0.4 meq./g, preferably ranging from 0.001 to 0.2 meq./g and more particularly ranging from 0.01 to 0.1 meq./g.
  • the amine number is the number of milli-equivalents of amine per gram of compound. This number is determined in an entirely conventional manner via titration methods with coloured indicator or via potentiometric titration.
  • a silicone corresponding to this formula is, for example, DC2-8299 from Dow Corning, sold in the form of a cationic emulsion.
  • Rs represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-C 18 alkyl or C 2 -Ci 8 alkenyl radical, for example methyl;
  • Re represents a divalent hydrocarbon-based radical, in particular a Ci-Ci 8 alkylene radical or a divalent CrCi 8 , for example C 1 -C 8 , alkyleneoxy radical linked to the Si via an SiC bond;
  • Q " is an anion such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.); r represents an average statistical value from 2 to 20 and in particular from 2 to 8; s represents an average statistical value from 20 to 200 and in particular from 20 to 50.
  • halide ion in particular chloride, or an organic acid salt (acetate, etc.)
  • r represents an average statistical value from 2 to 20 and in particular from 2 to 8
  • s represents an average statistical value from 20 to 200 and in particular from 20 to 50.
  • a silicone falling within this category is the silicone sold in the form of a cationic emulsion by the company Union Carbide under the name "Ucar Silicone ALE 56".
  • R 7 which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C 1 -C 18 alkyl radical, a C 2 -C 18 alkenyl radical or a ring containing 5 or 6 carbon atoms, for example methyl;
  • R 6 represents a divalent hydrocarbon-based radical, in particular a C 1 -Ci 8 alkylene radical or a divalent C 1 -C 18 , for example C 1 -C 8 , alkyleneoxy radical linked to the Si via an SiC bond;
  • R 8 which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C 1 -C 18 alkyl radical, a C 2 -C 18 alkenyl radical or a radical -R 6 -NHCOR 7 ;
  • X- is an anion such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.); r represents an average statistical value from 2 to 200 and in particular from 5 to 100.
  • Silicones falling within this category are the silicones sold in solution in propylene glycol by the company Goldschmidt under the names Abil ® Quat 3270, Abil ® Quat 3272 and Abil ® Quat 3474.
  • R 1 , R 2 , R 3 and R 4 which may be identical or different, denote a C 1 -C 4 alkyl radical or a phenyl group, - R 5 denotes a C 1 -C 4 alkyl radical or a hydroxyl group,
  • - n is an integer ranging from 1 to 5
  • - m is an integer ranging from 1 to 5, and in which x is chosen such that the amine number is between 0.01 and 1 meq./g.
  • n and n are numbers such that the sum (n + m) can range especially from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200, n possibly denoting a number from 0 to 999, especially from 49 to 249 and more particularly from 125 to 175 and m possibly denoting a number from 1 to 1000, especially from 1 to 10 and more particularly from 1 to 5;
  • R 1 , R 2 and R 3 which may be identical or different, represent a hydroxyl or C 1 -C 4 alkoxy radical, at least one of the radicals R 1 to R 3 denoting an alkoxy radical.
  • the alkoxy radical is a methoxy radical.
  • the hydroxyl/alkoxy mole ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and is more particularly equal to 0.3.
  • the amino silicone of formula (XIII) has a weight-average molecular mass preferably ranging from 2000 to 1 000 000 and even more particularly from 3500 to 200 000;
  • R 1 and R 2 which are different, represent a hydroxyl or C 1 -C 4 alkoxy radical, at least one of the radicals R 1 and R 2 denoting an alkoxy radical.
  • the alkoxy radical is a methoxy radical.
  • the hydroxyl/alkoxy mole ratio preferably ranges from 1 :0.8 to 1 :1.1 and preferably from 1 :0,9 to 1 :1 and is more particularly equal to 1 :0.95.
  • the amino silicone of formula (XIV) has a weight-average molecular mass preferably ranging from 2000 to 200 000, more particularly from 5000 to 100 000 and more particularly from 10 000 to 50 000.
  • the commercial products corresponding to these silicones of structure (XIII) or (XIV) may include in their composition one or more other amino silicones whose structure is different from structures (XIII) and (XIV).
  • a product containing amino silicones of structure (XIII) is sold by the company Wacker under the name Belsil ® ADM 652.
  • a product containing amino silicones of structure (XIV) is sold by the company Wacker under the name Fluid WR 1300 ® .
  • amino silicone microemulsions of formula (XIV) sold under the names Finish CT 96 E ® or SLM 28020 ® by the company Wacker may also be used.
  • the weight-average molecular masses of all these amino silicones are measured by gel permeation chromatography (GPC) at room temperature, as polystyrene equivalents.
  • the columns used are ⁇ styragel columns.
  • the eluent is THF and the flow rate is 1 ml/minute. 200 ⁇ l of a solution containing 0.5% by weight of silicone in THF are injected. Detection is performed by refractometry and UV-metry.
  • silicones that are particularly preferred in accordance with the invention are:
  • polysiloxanes containing amine groups such as amodimethicones, including trimethylsilyl- amodimethicones.
  • the amino silicone(s) may represent from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight and more particularly from 0.1% to 3% by weight relative to the total weight of the final composition.
  • the suitable dyeing medium generally consists of water or of a mixture of water and of at least one organic solvent to dissolve the compounds that are not sufficiently water- soluble.
  • organic solvents include C 1 -C 4 lower alkanols, such as ethanol and isopropanol; aromatic alcohols, for instance benzyl alcohol, and also similar products and mixtures thereof.
  • the solvents may be present in proportions preferably between 1% and 40% by weight approximately and even more preferentially between 5% and 30% by weight approximately relative to the total weight of the dye composition.
  • the pH of the dye composition in accordance with the invention is generally between 2 and 3
  • examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
  • 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 (XV) below:
  • R 3 , R 4 , R 5 and R 6 which may be identical or different, represent a hydrogen atom or a C 1 -C 6 alkyl or C 1 -C 6 hydroxyalkyl radical.
  • the dye composition in accordance with the invention may contain one or more additional direct dyes that may be chosen, for example, from nitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, xanthene dyes and non-cationic azo dyes.
  • the dye composition in accordance with the invention contains, in addition to the cationic direct dye(s) (i), one or more oxidation bases chosen from the oxidation bases conventionally used for oxidation dyeing, and among which mention may be made especially of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
  • R- I represents a hydrogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical, a (C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl radical, a C 1 -C 4 alkyl radical substituted with a nitrogenous group, a phenyl group or a 4'-aminophenyl group;
  • R 2 represents a hydrogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical, a (C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl radical or a C 1 -C 4 alkyl radical substituted with a nitrogenous group;
  • R 1 and R 2 may also form with the nitrogen atom that bears them a 5- or 6-membered nitrogenous heterocycle optionally substituted with one or more alkyl, hydroxy or ureido groups;
  • R 3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a Ci-C 4 alkyl radical, a sulfo radical, a carboxy radical, a Ci-C 4 monohydroxyalkyl radical, a Ci-C 4 hydroxyalkoxy radical, an acetylamino(Ci-C 4 )alkoxy radical, a CrC 4 mesylaminoalkoxy radical or a carbamoylamino(Ci-C 4 )alkoxy radical,
  • a halogen atom such as a chlorine atom, a Ci-C 4 alkyl radical, a sulfo radical, a carboxy radical, a Ci-C 4 monohydroxyalkyl radical, a Ci-C 4 hydroxyalkoxy radical, an acetylamino(Ci-C 4 )alkoxy radical, a CrC 4 mesylaminoalkoxy radical or a carbamoylamino(Ci-
  • R 4 represents a hydrogen or halogen atom or a CrC 4 alkyl radical.
  • nitrogenous groups of formula (XVI) above mention may be made in particular of amino, mono(Ci-C 4 )alkylamino, di(Ci-C 4 )alkylamino, tri(CrC 4 )alkylamino, monohydroxy(Ci- C 4 )alkylamino, imidazolinium and ammonium radicals.
  • para-phenylenediamines of formula (XVI) above examples include para-phenylenediamine, para-tolylenediamine, 2-chloro-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylene diamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N 1 N- dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis( ⁇ -hydroxyethyl)-para- phenylenediamine, 4-amino-N,N-bis( ⁇ -hydroxyethyl)-2-methylaniline, 4-amino-2-chloro-N
  • para-phenylenediamine para- tolylenediamine, 2-isopropyl-para-phenylenediamine, 2- ⁇ -hydroxyethyl-para-phenylene- diamine, 2- ⁇ -hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis( ⁇ -hydroxy- ethyl)-para-phenylenediamine and 2-chloro-para-phenylenediamine, and the addition salts thereof with an acid are most particularly preferred.
  • double bases is understood to refer to the compounds containing at least two aromatic nucleii bearing amino and/or hydroxyl groups.
  • double bases that may be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made in particular of the compounds corresponding to formula (XVII) below, and the addition salts thereof with an acid:
  • - Z 1 and Z 2 which may be identical or different, represent a hydroxyl or -NH 2 group that may be substituted with a Ci-C 4 alkyl radical or with a linker arm Y;
  • the linker arm Y represents a linear or branched alkylene chain containing from 1 to 14 carbon atoms, which may be interrupted by or terminated with one or more nitrogenous groups and/or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and optionally substituted with one or more hydroxyl or C 1 -C 6 alkoxy radicals;
  • R 5 and R 6 represent a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical, a C 1 -C 4 aminoalkyl radical or a linker arm Y;
  • R 7 , R 8 , Rg, Rio > Rn and Ri 2 which may be identical or different, represent a hydrogen atom, a linker arm Y or a C 1 -C 4 alkyl radical; it being understood that the compounds of formula (XVII) contain only one linker arm Y per molecule.
  • nitrogenous groups of formula (XVII) above mention may be made in particular of amino, mono(CrC 4 )alkylamino, di(C r C 4 )alkylamino, tri(C r C 4 )alkylamino, monohydroxy(Ci-C 4 )alkylamino, imidazolinium and ammonium radicals.
  • N,N'-bis( ⁇ -hydroxyethyl)-N,N'-bis(4'-amino- phenyl)-1 ,3-diaminopropanol and 1 ,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or one of the addition salts thereof with an acid are particularly preferred.
  • R 13 represents a hydrogen atom, a halogen atom such as fluorine, a Ci-C 4 alkyl, C 1 -C 4 monohydroxyalkyl, (C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl, C 1 -C 4 aminoalkyl or hydroxy(C 1 -C 4 )alkylamino(C 1 -C 4 )alkyl radical,
  • Ri 4 represents a hydrogen atom or a halogen atom such as fluorine, a Ci-C 4 -alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl, Ci-C 4 cyanoalkyl or (C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl radical.
  • para-aminophenols of formula (XVIII) mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino- 3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino- 2-methoxymethylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-
  • the ortho-aminophenols that may be used as oxidation bases in the context of the present invention are chosen especially from 2-aminophenol, 2-amino-1-hydroxy-5- methylbenzene, 2-amino-1-hydroxy-6-methylbenzene and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
  • heterocyclic bases that may be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made more particularly of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and the addition salts thereof with an acid.
  • pyridine derivatives mention may be made more particularly of the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxy pyridine, 2-( ⁇ -methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine, and the addition salts thereof with an acid.
  • pyrimidine derivatives mention may be made more particularly of the compounds described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine and 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made especially of pyrazolo[1 ,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1 ,5-a] pyrimidine-3,7-diamine; pyrazolo[1 ,5-a]pyrimidine-3,5-diamine; 2,
  • pyrazole derivatives mention may be made more particularly of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3-dimethyl- pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, A- amino-1 ,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5- diamino-3-tert-butyl-1-methylpyrazole, 4,5
  • the oxidation base(s) preferably represent(s) from 0.0005% to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005% to 6% by weight approximately relative to this weight.
  • the dye composition in accordance with the invention may also contain, in addition to the cationic direct dye (i) and the amino silicone (ii) and also oxidation bases, one or more couplers so as to modify or to enrich with tints the shades obtained using the cationic direct dye(s) (i) and the oxidation base(s).
  • the couplers that may be used in the dye composition according to the invention are those conventionally used in oxidation dye compositions, i.e. meta-aminophenols, meta- phenylenediamines, meta-diphenols, naphthols and heterocyclic couplers, for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3-benzodioxoles, quinolines and the addition salts thereof with an acid.
  • meta-aminophenols i.e. meta-aminophenols, meta- phenylenediamines, meta-diphenols, naphthols and heterocyclic couplers
  • indole derivatives indoline derivatives, sesamol and derivatives thereof
  • pyridine derivatives
  • couplers are more particularly chosen from 2,4-diamino-1-( ⁇ - hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-( ⁇ -hydroxyethyl)amino-2-methyl- phenol, 3-aminophenol, 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 4-chloro- 1 ,3-dihydroxybenzene, 2-amino-4-( ⁇ -hydroxyethylamino)-1 -methoxybenzene, 1 ,3- diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, sesamol, 1-amino-2-methoxy-4,5- methylenedioxybenzene ⁇ -naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methyl- indole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine
  • addition salts with an acid of the oxidation bases and couplers are especially chosen from the hydrochlorides, hydrobromides, sulfates, tartrates, lactates and acetates.
  • the coupler(s) preferably represent(s) from 0.0001% to 10% by weight approximately relative to the total weight of the dye composition, and even more preferentially from 0.005% to 5% by weight approximately relative to this weight.
  • the dye composition in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as antioxidants, penetrants, sequestrants, fragrances, buffers, nonionic, anionic or amphoteric polymers, non-silicone cationic polymers, nonionic, cationic or amphoteric surfactants, ceramides, preserving agents, screening agents and opacifiers.
  • adjuvants conventionally used in hair dye compositions such as antioxidants, penetrants, sequestrants, fragrances, buffers, nonionic, anionic or amphoteric polymers, non-silicone cationic polymers, nonionic, cationic or amphoteric surfactants, ceramides, preserving agents, screening agents and opacifiers.
  • the dye composition according to the invention may be in various forms, such as in the form of liquids, shampoos, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair. It may be obtained by extemporaneously mixing a composition, optionally a pulverulent composition, containing the cationic direct dye(s) with a composition containing at least one oxidation base and at least one amino silicone.
  • the dye composition in accordance with the invention also contains at least one oxidizing agent chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases, laccases and two-electron oxidoreductases.
  • oxidizing agent chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases, laccases and two-electron oxidoreductases.
  • the use of hydrogen peroxide or of enzymes is particularly preferred.
  • Another subject of the invention is a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.
  • At least one dye composition as defined above is applied to the fibres for a time that is sufficient to develop the desired coloration, after which the fibres are rinsed, optionally washed with shampoo, rinsed again and dried.
  • the time required to develop the coloration on the keratin fibres is generally between 3 and 60 minutes and even more precisely between 5 and 40 minutes.
  • At least one dye composition as defined above is applied to the fibres for a time that is sufficient to develop the desired coloration, without final rinsing.
  • the dyeing process comprises a preliminary step that consists in separately storing, on the one hand, a composition (A1) comprising, in a suitable dyeing medium, at least one cationic direct dye (i) as defined above and, on the other hand, a composition (B1 ) containing, in a suitable dyeing medium, at least one oxidizing agent, and then in mixing them together at the time of use, followed by applying this mixture to the keratin fibres, composition (A1 ) or composition (B1) containing at least one amino silicone as defined above.
  • a composition (A1) comprising, in a suitable dyeing medium, at least one cationic direct dye (i) as defined above
  • a composition (B1 ) containing, in a suitable dyeing medium, at least one oxidizing agent and then in mixing them together at the time of use, followed by applying this mixture to the keratin fibres, composition (A1 ) or composition (B1) containing at least one amino silicone as defined above.
  • the dyeing process includes a preliminary step that consists in separately storing, on the one hand, a composition (A2) comprising, in a suitable dyeing medium, at least one cationic direct dye (i) as defined above and at least one oxidation base, and, on the other hand, a composition (B2) containing, in a suitable dyeing medium, at least one oxidizing agent, and then in mixing them together at the time of use, followed by applying this mixture to the keratin fibres, composition (A2) or composition (B2) containing at least one amino silicone (ii) as defined above.
  • a preliminary step that consists in separately storing, on the one hand, a composition (A2) comprising, in a suitable dyeing medium, at least one cationic direct dye (i) as defined above and at least one oxidation base, and, on the other hand, a composition (B2) containing, in a suitable dyeing medium, at least one oxidizing agent, and then in mixing them together at the time of use, followed by applying this mixture to the
  • Another subject of the invention is a multi-compartment device or dyeing "kit” or any other multi-compartment packaging system, of which a first compartment contains composition (A1) or (A2) as defined above, and a second compartment contains composition (B1) or (B2) as defined above.
  • These devices may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR 2 586 913 in the name of the Applicant.
  • the dye composition below was prepared (amounts expressed as grams of active material):
  • composition was applied firstly to locks of natural grey hair containing 90% white hairs, and secondly to locks of permanent-waved grey hair containing 90% white hairs, for 30 minutes at room temperature (2O 0 C).
  • the locks are rinsed, shampooed and then rinsed and dried. They are dyed in a sparingly selective very chromatic violet-blue shade.
  • Example 1 A similar result to that of Example 1 is obtained by replacing dye 1 weight for weight with dye 2 and the amino silicone emulsion Dow Corning 8299 with the amino silicone SLM 28020® sold by the company Wacker.

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Abstract

The invention relates to a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising, in a suitable dyeing medium, at least one tetraazapentamethine cationic direct dye, and which is characterized in that it also contains at least one amino silicone. The invention also relates to the processes and dyeing devices using the said composition.

Description

COMPOSITION FOR DYEING KERATIN FIBRES WITH A TETRAAZAPENTAMETHINE CATIONIC DIRECT DYE AND AN AMINO SILICONE
The invention relates to a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising, in a suitable dyeing medium, at least one tetraazapentamethine cationic direct dye, and which is characterized in that it also contains at least one amino silicone.
The invention also relates to the processes and dyeing devices using the said composition.
Two types of dyeing may be distinguished in the field of hair dyeing.
The first is semi-permanent or temporary dyeing, or direct dyeing, which involves dyes capable of giving the hair's natural coloration a more or less pronounced colour change, which may be resistant to shampoo washing several times. These dyes are known as direct dyes; they may be used with or without an oxidizing agent. In the presence of an oxidizing agent, the aim is to obtain lightening dyeing. Lightening dyeing is performed by applying to the hair an extemporaneous mixture of a direct dye and an oxidizing agent, and makes it possible especially to obtain, via lightening of the melanin of the hair, an advantageous effect such as a unified colour in the case of grey hair, or to bring out the colour in the case of naturally pigmented hair.
The second is permanent dyeing or oxidation dyeing. This is performed with "oxidation" dyes comprising oxidation dye precursors and couplers. Oxidation dye precursors, commonly known as "oxidation bases", are compounds that are initially colourless or weakly coloured, which develop their dyeing power on the hair in the presence of oxidizing agents added at the time of use, leading to the formation of coloured compounds and dyes. The formation of these coloured compounds and dyes results either from an oxidative condensation of the "oxidation bases" with themselves, or from an oxidative condensation of the "oxidation bases" with coloration modifiers commonly known as "couplers", which are generally present in the dye compositions used in oxidation dyeing.
To vary the shades obtained with the said oxidation dyes, or to enrich them with tints, direct dyes may be added thereto.
Among the already known cationic direct dyes available in the field of dyeing keratin fibres, especially human keratin fibres, are tetraazapentamethine compounds, the structure of which is discussed in the text hereinbelow; however, these dyes lead to colorations which have characteristics that are still insufficient as regards the strength and the homogeneity of the colour distributed along the fibre: the coloration is then said to be too selective, and as regards the staying power in terms of resistance to the various attacking factors to which the hair may be subjected (light, bad weather, shampooing).
Now, after considerable research conducted in this matter, the Applicant has discovered that it is possible to obtain novel compositions for dyeing keratin fibres, which are capable of leading to strong and sparingly selective colorations, but which nevertheless withstand the various attacking factors to which the hair may be subjected, by combining at least one particular silicone with at least one tetraazapentamethine cationic direct dye known in the prior art and with the formulae respectively defined hereinafter.
This discovery is the basis of the present invention.
A first subject of the present invention is thus a composition for dyeing keratin fibres and in particular human keratin fibres such as the hair, containing, in a suitable dyeing medium, (i) at least one cationic direct dye whose structure corresponds to formula (I) defined below, characterized in that it also contains (ii) at least one amino silicone:
Figure imgf000003_0001
in which
W1 represents a cationic heteroaromatic radical of formula (II) or (III):
Figure imgf000003_0002
(H) m
W2 represents a heteroaromatic radical of formula (IV) or (V):
Figure imgf000003_0003
(TV) CO in which:
Z0 represents a radical CR2, a nitrogen atom or a radical NR21, Z1 represents an oxygen or sulfur atom or a radical NR9,
Z2 represents a nitrogen atom or a radical CR10,
Z3 represents a nitrogen atom or a radical CRn,
Z4 represents a nitrogen atom or a radical CR12, - Z5 represents a nitrogen atom or a radical CR13,
Z6 represents a nitrogen atom or a radical CR14,
Z7 represents an oxygen or sulfur atom or a radical NR15,
Z8 represents a nitrogen atom or a radical CR16,
Z9 represents a nitrogen atom or a radical CR17, - Z10 represents a nitrogen atom or a radical CR18,
Z11 represents a nitrogen atom or a radical CR19,
Z12 represents a nitrogen atom or a radical CR20,
Z13 represents a radical CR6, a nitrogen atom or a radical NR22, it being understood that each of the rings of formulae (II), (III), (IV) and (V) comprise not more than three nitrogen atoms and that two of the three nitrogen atoms may be contiguous, the bond a of the 5-membered cationic heteroaromatic radical of formula (II) being linked to the nitrogen atom N1 of formula (I), the bond b of the 6-membered cationic heteroaromatic radical of formula (III) being linked to the nitrogen atom N1 of formula (I), the double bond a' of the 5-membered heteroaromatic radical of formula (IV) being linked to the nitrogen atom N2 of formula (I), the double bond b' of the 6-membered heteroaromatic radical of formula (V) being linked to the nitrogen atom N2 of formula (I), - the bond b, linking the cationic heteroaromatic radical of formula (III) to the nitrogen atom N1 of formula (I), being in an ortho or para position relative to the nitrogen atom bearing the radical R4 when Z5 represents a radical CR13; the bond b being in an ortho position relative to the nitrogen atom bearing the radical R4 when Z5 represents a nitrogen atom, - the bond b', linking the heteroaromatic radical of formula (V) to the nitrogen atom N2 of formula (I), being in an ortho or para position relative to the nitrogen atom bearing the radical R7 when Zi1 represents a radical CR19; the bond b' being in an ortho position relative to the nitrogen atom bearing the radical R7 when Z11 represents a nitrogen atom, - R2, R6, R10 and Ri6 represent, independently of each other, a hydrogen atom; a linear or branched C1-C4 alkyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, Ci-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2
(di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino and CrC2 (di)alkylamino radicals; a carboxyl radical; a sulfonylamino radical,
Ri, R4, R5, R7, Rg, Ri5, R21 and R22 represent, independently of each other, a linear or branched C1-C8 alkyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals;
R0, R3, Re, R11, R12, Ri3, Ri4. Ri7> R18. Ri9 and R2o represent, independently of each other, a hydrogen atom, a linear or branched C1-C16 hydrocarbon-based chain, this chain possibly being saturated or unsaturated with one to three unsaturations, this chain being unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl, sulfonic, sulfonylamino and C2-C4 (poly)hydroxyalkylamino radicals or a halogen atom such as chlorine, fluorine or bromine; a phenyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl, sulfonic, sulfonylamino and C2-C4 (poly)hydroxyalkylamino radicals or a halogen atom such as chlorine, fluorine or bromine; a heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl and pyridazinyl radicals; in addition, this hydrocarbon-based chain may be interrupted with one or two oxygen, nitrogen or sulfur atoms or with an SO2 radical, it being understood that R0, R3, Rs, Rn, R12, R13, R14, R17, R18, R19 and R20 do not comprise a peroxide bond or diazo or nitroso radicals,
R2 with R10, R1-I with R12, R6 with R16, and R17 with R18 can form, independently of each other, a 5- or 6-membered carbon-based aromatic ring, which is unsubstituted or substituted with one or two hydroxyl, amino, (di)(C1-C2)alkylamino, C1-C2 alkoxy or C2-C4 (poly)hydroxyalkylamino radicals, X is an organic or mineral anion.
For the purposes of the present patent application, the expression "branched hydrocarbon- based chain" means a branched hydrocarbon-based chain that may also form one to five 3- to 7-membered carbon-based rings, this chain possibly comprising one to three unsaturations, i.e. one to three double bonds and/or triple bonds.
The term "C2-C4 (poly)hydroxyalkoxy" means a C2-C4 alkoxy group substituted with 1 or 2 hydroxyl groups.
For the purposes of the present invention, the expression "C2-C4 (poly)hydroxyalkylamino" means an alkylamino group substituted with 1 or 2 hydroxyl groups.
The expression according to which the hydrocarbon-based chain may be interrupted with one or more oxygen, nitrogen or sulfur atoms or with an SO2 radical, or according to which this chain is unsaturated, means that the carbon-based chain may be modified in the following manner:
|~— CHj— H can become — Q-H
Figure imgf000006_0001
J-CHr-CH3 can become [-O-CH,
For the purposes of the present patent application, an organic or mineral anion is chosen, for example, from a halide such as chloride, bromide, fluoride or iodide; a hydroxide; a sulfate; a hydrogen sulfate; a (d-C6)alkyl sulfate, for instance a methyl sulfate or an ethyl sulfate; an acetate; a tartrate; an oxalate; a (Ci-C6)alkylsulfonate such as methyl sulfonate; an aryisulfonate, which is unsubstituted or substituted with a C1-C4 alkyi radical, for instance a 4- tolylsulfonate.
Preferably, R0 represents a hydrogen atom; a linear or branched Ci-C6 alkyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, CrC2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, C2-C4 (poly)hydroxyalkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, Ci-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, Ci-C2 (di)aikylamino, carboxyl and sulfonic radicals or a halogen atom such as chlorine, fluorine or bromine, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl and pyridazinyl radicals.
Even more preferably, R0 preferably represents a hydrogen atom; a linear or branched Ci-C3 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C1-C2 alkoxy, amino, Ci-C2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, C1-C2 (di)alkylamino and C2-C4 (poly)hydroxyalkylamino radicals, or an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl and pyridyl radicals.
According to one particularly preferred embodiment, R0 represents a hydrogen atom; a methyl, ethyl, propyl, butyl, 2-hydroxyethyl, 2-aminoethyl, 1-carboxy methyl, 2-carboxyethyl, 2-sulfonylethyl or 2-methoxyethyl; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from amino, Ci-C2 (di)alkylamino and C2-C4 (poly)hydroxyalkylamino radicals, or an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl and pyridyl radicals.
R0 even more preferably represents a hydrogen atom; a methyl, ethyl or 2-methoxyethyl radical; a phenyl radical, which is unsubstituted or substituted with an amino, (di)methylamino or (di)(2-hydroxyethyl)amino radical, or an optionally cationic heteroaryl radical chosen from imidazolyl and pyridyl radicals.
R2, R6, R10 and Ri6 preferably represent a hydrogen atom, a phenyl radical or a CrC4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, CrC2 (di)alkylamino and carboxyl radicals.
According to one particularly preferred embodiment, R2, R6, R10 and Ri6 preferably represent a hydrogen atom, a methyl, phenyl or 2-hydroxymethyl radical, a carboxyl or a phenyl radical.
Ri, R4, R5, R7, Rg, Ri5> R21 and R22 preferably represent a CrC4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, CrC2 alkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals.
According to one particularly preferred embodiment, R1, R4, R5, R7, R9, Ri5, R2i and R22 preferably represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl or 2- sulfonylethyl radical.
R3, R8, R11, R12, R13, R14, Ri7, R18, R19 and R20 preferably represent, independently of each other, a hydrogen atom; a linear or branched Ci-C4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, Ci-C2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, Ci-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals or a halogen atom such as chlorine, fluorine or bromine; a sulfonylamino radical; a C2-C4 (poly)hydroxyalkylamino radical.
More preferably, R3, R8, Rn, R12, R13, Ru, R17, Riβ> R19 and R2o represent a hydrogen atom, a C1-C4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl radicals or a C1-C2 alkoxy radical; an amino radical; a C1-C2 (di)alkylamino radical; a carboxyl radical; a C2-C4 (poly)hydroxyalkylamino radical.
According to one particularly preferred embodiment, R3, R8, R-π, R12, R13, R14, R17, R18, Ri9 and R20 represent, independently of each other, a hydrogen atom, a methyl or 2- hydroxymethyl radical, a carboxyl, a methoxy, ethoxy or 2-hydroxyethyloxy radical, or an amino, methylamino, dimethylamino or 2-hydroxyethylamino radical.
A. In a first preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-pyridinium radical and W2 is a 2-pyridine radical. Even more preferably, they are the following compounds:
- 2-[5-(N-methyl-2-pyridinylidene)-1-formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-methyl-1 -formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-ethyl-1 -formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-N-methylpyridinium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-phenyl-1-formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N-methylpyridinium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-N- methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-1-formazano]-4-pyrrolidino-N- methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-methyl-1-formazano]-4-pyrrolidino-N- methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-ethyl-1-formazano]-4-pyrrolidino-N- methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-isopropyl-1-formazano]-4-pyrrolidino-N- methylpyridinium chloride - 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-phenyl-1-formazano]-4-pyrrolidino-N- methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-4- pyrrolidino-N-methylpyridinium chloride - 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-4- pyrrolidino-N-methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-4-pyrrolidino-N-methylpyridinium chloride - 2-[5-(N-hydroxyethyl-2-pyridinylidene)-1-formazano]-N-hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-methyl-1-formazano]-N-hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-ethyl-1-formazano]-N-hydroxyethylpyridinium chloride - 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-phenyl-1 -formazano]-N-hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-isopropyl-1-formazano]-N-hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-N- hydroxyethylpyridinium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-1-formazano]-N-carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-methyl-1-formazano]-N-carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-ethyl-1-formazano]-N-carboxyethylpyridinium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-phenyl-1 -formazano]-N-carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-isopropyl-1-formazano]-N-carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-N- carboxyethylpyridinium chloride
B. In a second preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 4-pyridinium radical and W2 is a 4-pyridine radical. Even more preferably, they are the following compounds: - 4-[5-(N-methyl-4-pyridinylidene)-1-formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-methyl-1 -formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-ethyl-1 -formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-N-methylpyridinium chloride - 4-[5-(N-methyl-4-pyridinylidene)-3-phenyl-1-formazano]-N-methylpyridiriium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N-methylpyridinium chloride - 4-[5-(N-methyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-N- methylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-1 -formazano]-N-hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-N-hydroxyethylpyridinium chloride - 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-ethyl-1-formazano]-N-hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-N-hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-isopropyl-1-formazano]-N-hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- hydroxyethylpyridinium chloride - 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-N- hydroxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-1-formazano]-N-carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-N-carboxyethylpyridinium chloride - 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-ethyl-1 -formazano]-N-carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-N-carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-isopropyl-1-formazano]-N-carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-N- carboxyethylpyridinium chloride
C. In a third preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-imidazolium radical and W2 is a 2-imidazole radical. Even more preferably, they are the following compounds:
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-1 -formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-methyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-ethyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-isopropyl-1 -formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-phenyl-1-forrnazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride - 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-1 -formazano]-1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-methyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-ethyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride - 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-isopropyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- 1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-1-formazano]-1 ,3-dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-methyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-ethyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-phenyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-isopropyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- 1 ,3-dicarboxyethylimidazolium chloride
D. In a fourth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 5-pyrazolium radical and W2 is a 5-pyrazole radical. Even more preferably, they are the following compounds: - 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-1-formazano]-1 ,2-dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-methyl-1 -formazano]-1 ,2-dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-ethyl-1 -formazano]-1 ,2-dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-isopropyl-1-formazano]-1 ,2-dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-phenyl-1 -formazano]-1 ,2-dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,2- dimethylpyrazolinium chloride - 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,2- dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,2- dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-1-formazano]-1 ,2-dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-methyl-1-formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-ethyl-1-formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-phenyl-1 -formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-isopropyl-1 -formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,2- dihydroxyethylpyrazolinium chloride - 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- 1 ,2-dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-1 -formazano]-1 ,2-dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-methyl-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-ethyl-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-phenyl-1-formazano]-1 ,2- dicarboxyethylpyrazolinium chloride - 5-[5-(1,2-dicarboxyethyl-5-pyrazolidene)-3-isopropyl-1-formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- δ-tδ-CI ^-dicarboxyethyl-δ-pyrazolidene^S^'-N.N-dimethylaminophenyO-i-formazano]- 1 ,2-dicarboxyethylpyrazolinium chloride
E. In a fifth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-benzimidazolium radical and W2 is a 2- pyridine radical. Even more preferably, they are the following compounds:
- 2-[5-(N-methyl-2-pyridinylidene)-1-formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-methyl-1 -formazano]-1 ,3-dimethylbenzimidazolium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-isopropyl-1-formazano]-1 ,3-dimethylbenzimidazolium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1,3- dimethylbenzimidazoϋum chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-1 -formazano]-1 ,3-dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-1-formazano]-1 ,3-dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-ethyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-isopropyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
F. In a sixth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-benzimidazolium radical and W2 is a A- pyridine radical. Even more preferably, they are the following compounds:
- 2-[5-(N-methyl-4-pyridinylidene)-1-formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-methyl-1 -formazano]-1 ,3-dimethylbenzimidazolium chloride - 2-[5-(N-methyl-4-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-isopropyl-1-formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-phenyl-1-formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride - 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-1-formazano]-1 ,3-dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-isopropyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-1-formazano]-1 ,3-dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-ethyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
G. In a seventh preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-imidazolium radical and W2 is a 2-pyridine radical. Even more preferably, they are the following compounds: - 2-[5-(N-methyl-2-pyridinylidene)-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-methyl-1-formazano]-1 ,3-dimethylimidazoliurn chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-ethyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3-dimethylimidazolium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-phenyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-1-formazano]-1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-1-formazano]-1,3-dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dicarboxyethyiimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dicarboxyethyiimidazolium chloride
H. In an eighth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-imidazolium radical and W2 is a 4-pyridine radical. Even more preferably, they are the following compounds: - 2-[5-(N-methyl-4-pyridinylidene)-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-methyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-ethyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-isopropyl-1-formazano]-1 ,3-dimethylimidazolium chloride - 2-[5-(N-methyl-4-pyridinylidene)—3-phenyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride - 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)r1-formazano]-1,3- dimethylimidazolium chloride - 2-[5-(N-hydroxyethyl-4-pyridinylidene)-1-formazano]-1,3-dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride - 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-1-formazano]-1 ,3-dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-ethyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-1,3- dicarboxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
I. In a ninth preferred variant, the compounds of formula I are chosen from the family defined by the compounds for which W1 is a 2-benzimidazolium radical and W2 is a 2-benzimidazole radical. Even more preferably, they are the following compounds:
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-1-formazano]-1 ,3-dimethylbenzimidazolium chloride - 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-methyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-ethyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-isopropyl-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-phenyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dimethylbenzimidazolium chloride - 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- 1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-methyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-phenyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dihydroxyethylbenzimidazolium chloride - 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-methyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-ethyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-phenyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-isopropyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-(4'-hydroxyphenyl)-1-formazano]-1,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dicarboxyethylbenzimidazolium chloride.
Among all the compounds described above, the compounds of family A (first variant) will be preferred most particularly.
In the compositions of the invention, the compound(s) of formula (I) is (are) preferably present in a concentration ranging from 0.001% to 10%, preferably from 0.005% to 5% and even more preferentially from 0.01% to 2% by weight relative to the total weight of the composition.
The compounds of formula (I) may especially be obtained via a process in which at least two equivalents of at least one hydrazone chosen from the hydrazones of formula A and the hydrazones of formula B:
Figure imgf000020_0001
HT
Formula A Formula B
in which Z14, Z15, Z16 and R25 have the same meanings as Z7, Z8, Z13, and R5, respectively, of formula IV,
Y being an organic or mineral anion, x being an integer ranging from 1 to 3, Z17, Z18, Z19, Z20, R26 and R27 have the same meanings as Z9, Z10, Z11, Z12, R8 and R7, respectively, of formula V,
Y' being an organic or mineral anion, x' being an integer ranging from 1 to 3, are reacted with one equivalent of an aldehyde of formula R23CHO, R23 having the same meaning as Ro of formula I. Two equivalents of the same hydrazone or of two different hydrazones may thus be reacted.
According to one preferred variant, the aldehyde of formula R23CHO is generated in the reaction medium from an aldehyde precursor of formula R'23CH2OH in the presence of an oxidizing system; R'23 then has the same meaning as R0 of formula I.
This oxidizing system may be a chemical oxidizing agent or a biocatalytic oxidizing agent such as an enzyme.
In particular, the process for preparing the compound of formula (I) according to the present invention may be performed in the presence of an aldehyde precursor of formula R'23CH2OH and of at least one enzyme capable of generating an aldehyde from the aldehyde precursor of formula R'23CH2OH.
The process for enzymatically synthesizing the compounds of formula (I) defined above is performed by reacting at least two equivalents of at least one hydrazone chosen from the hydrazones of formula A and the hydrazones of formula B in which Z14, Z15, Zi6 and R25 have the same meanings as Z7, Z8, Zi3 and R5, respectively, of formula IV,
Y being an organic or mineral anion, x being an integer ranging from 1 to 3,
Z17, Z18, Z19, Z20, R26 and R27 having the same meanings as Z9, Zi0, Z11, Z12, R8 and R7, respectively, of formula V, Y' being an organic or mineral anion, x' being an integer ranging from 1 to 3, with one equivalent of an aldehyde of formula R23CHO, R23 having the same meaning as R0 of formula I.
Depending on the reagents used, the reaction is performed with or without an oxidizing system, with or without a cofactor for the enzyme, and with or without a system for regenerating the cofactor.
For the purpose of the present patent application, the term "without an oxidizing system" means that no oxidizing system other than atmospheric oxygen is used.
Preferably, the reaction is performed in aerobic medium at a pH of between 3 and 11 and at a temperature of between 60C and 8O0C. More generally, the aldehyde precursor that may be used to prepare the compound of formula (I) may be chosen from primary alcohols, sarcosine, 4-hydroxymandelate, N6- methyllysine, dimethylglycine, methylglutamate, 2-oxo acids, for example 2-oxo acid pyruvate, benzoylformate, phenyl pyruvate or threonine. It will preferably be chosen from primary alcohols.
The enzymes capable of generating an aldehyde from this aldehyde precursor may be chosen especially from the alcohol dehydrogenases EC 1.1.1.1, the alcohol dehydrogenases EC 1.1.1.2, the alcohol dehydrogenases EC 1.1.1.71 , the aromatic alcohol dehydrogenases EC 1.1.1.90, also known as aryl alcohol dehydrogenases, the aromatic alcohol dehydrogenases EC 1.1.1.97, the 3-hydroxybenzyl alcohol dehydrogenases EC 1.1.1.97, the coniferyl alcohol dehydrogenases EC 1.1.1.194, the cinnamyl alcohol dehydrogenases EC 1.1.1.195, the methanol dehydrogenases EC 1.1.1.244, the aromatic alcohol oxidases EC 1.1.3.7, also known as aryl alcohol oxidases, the alcohol oxidases EC 1.1.3.13, the A- hydroxymandelate oxidases EC 1.1.3.19, the long-chain hydrocarbon alcohol oxidases EC 1.1.3.20, the methanol oxidases EC 1.1.3.31 , the alcohol dehydrogenases EC 1.1.99.20, the sarcosine oxidases EC 1.5.3.1 , the N6-methyllysine oxidases EC 1.5.3.4, the dimethylglycine oxidases EC 1.5.3.10, the sarcosine dehydrogenases EC 1.5.99.1 , the dimethylglycine dehydrogenases EC 1.5.99.2, the methylglutamate dehydrogenases EC 1.5.99.5, the 2-oxo acid decarboxylases EC 4.1.1.1 , the benzoylformate decarboxylases
EC 4.1.1.7, the phenylpyruvate decarboxylases EC 4.1.1.43 and the threonine aldolases EC 4.1.2.5.
Mention may also be made of the following enzymes capable of generating an aldehyde, the preferred substrate of which is given in parentheses: N-methyl L-amino acid oxidase EC 1.5.3.2 (N-methyl-L-amino acid), trimethylamine dehydrogenase EC 1.5.99.7 (trimethylamine), dimethylamine dehydrogenase EC 1.5.99.10 (dimethylamine), nitroethane oxidase EC 1.7.3.1 (nitroethane), indole 2,3-dioxigenase EC 1.13.11.17 (indole), taurine dioxygenase EC 1.14.11.17 (taurine), acetoin ribose 5 phosphate transaldolase EC 2.2.1.4 (3-hydroxybutan-2-one), diamine aminotransferase EC 2.6.1.29 (alpha omega diamine + 2- oxogluterate), alkenylglycerophosphocholine hydrolase EC 3.3.2.2
(alkenylglycerophosphocholine), alkenylglycerophosphoethanolamine hydrolase EC 3.3.2.5 (alkenylglycerophosphocholine), alkylalidase EC 3.8.1.1 (halomethane), phosphonoacetaldehyde hydrolase EC 3.11.1.1 (phosphonoacetaldehyde), indolepyruvate decarboxylase EC 4.1.1.74 (3-indol-3-yl pyruvate) mandelonitrile lyase EC 4.1.2.10 (mandelonitrile), hydroxymandelonitrile lyase EC 4.1.2.11 (hydroxymandelonitrile), ketopantoaldolase EC 4.1.2.12 (2-hydroxy-2-isopropylbutanedioate), dimethylaniline-N-oxide aldolase EC 4.1.2.24 (dimethylaniline-N-oxide), phenylserine aldolase EC 4.1.2.26 (phenylserine), sphinganine-1 -phosphate aldolase EC 4.1.2.27 (sphinganine-1 -phosphate), 17-alpha hydroxyprogesterone aldolase EC 4.1.2.30 (17-alpha hydroxyprogesterone), trimethylamine oxide aldolase EC 4.1.2.23 (trimethylamine oxide), fucosterol epoxide lyase EC 4.1.2.23 (fucosterol epoxide), (3E)-4-(2-carboxyphenyl)-2-oxobut-3-enoate aldolase EC 4.1.2.34 ((3E)-4-(2-carboxyphenyl)-2-oxobut-3-enoate), lactate aldolase EC 4.1.2.36 (lactate), benzoin aldolase EC 4.1.2.38 (benzoin), octoamine dehydratase EC 4.2.1.87 (1-(4- hydroxyphenyl)-2-aminoethanol), synephrine dehydratase EC 4.2.1.88 (1-(4-hydroxyphenyI)- 2-(methylamino)ethanol), ethanolamine phosphate phospholyase EC 4.2.3.2 (ethanolamine phosphate), ethanolamine ammonia lyase EC 4.3.1.7 (ethanolamine), dichloromethane dehalogenase EC 4.5.1.3 (dichloromethane), styrene oxide isomerase EC 5.3.99.7 (styrene oxide).
The enzyme capable of generating an aldehyde from the aldehyde precursor used in the dye composition according to the invention may be derived from an extract of plants, of animals, of microorganisms (bacterium, fungus, yeast or microalga) or from viruses, or from cells that are differentiated or undifferentiated, obtained in vivo or in vitro, which are genetically modified or unmodified, or synthetic (obtained via chemical or biotechnological synthesis).
Examples of useful enzymes that may be mentioned in particular are the genera Plectranthus, Pinus, Gastropode, Manduca, Pichia, Candida, Pleurotus, and Pseudomonas, and even more particularly the following species: Plectranthus colloides, Pinus strobus, which is a species of plant origin, Gastropode mollusc and Manduca sexta, which are of animal origin, Pichia pastoris and Candida boidinii, which are yeasts, Pleurotus pulmonarius, which is a fungus, and Pseudomonas pseudoalcaligenes, which is a bacterium.
The choice of the enzyme depends on the nature of the aldehyde precursor. For example, when the aldehyde precursor is an alcohol, then the enzyme is chosen from enzymes capable of generating an aldehyde from this alcohol. When the aldehyde precursor is methylglutamate, then the enzyme is a methylglutamate dehydrogenase.
According to one preferred variant, the aldehyde precursor is a primary alcohol and the enzyme is an enzyme capable of generating the aldehyde from an alcohol. For example, when the primary alcohol is a Ci-C6 aliphatic alcohol, then the enzyme capable of generating the aldehyde is chosen from alcohol oxidases, alcohol dehydrogenases, methanol dehydrogenases and methanol oxidases. When the primary alcohol is benzyl alcohol, 4-tert- butylbenzyl alcohol, 3-hydroxy-4-methoxybenzyl alcohol, veratryl alcohol, 4-methoxybenzyl alcohol, cinnamyl alcohol or 2,4-hexadien-1-ol, aryl alcohol oxidases or aromatic alcohol dehydrogenases may be used as aldehyde precursor. For the enzyme dehydrogenases, it is essential to include the cofactor(s) required for their activity, more specifically NAD+ or NADP+ or other molecules capable of acting as electron acceptor. The addition of a system for regenerating the cofactors may be used for reaction purposes or economic purposes. This regeneration system may be enzymatic, chemical or electrochemical.
A very wide variety of oxidizing agents may be used to perform this process: aqueous hydrogen peroxide solution, organic peracids such as peracetic acid, persalts such as permanganate, perborate and persulfates, chromates or dichromates, hypochlorites, hypobromites, ferricyanides, and peroxides such as manganese dioxide or lead dioxide. Aqueous hydrogen peroxide solution will preferably be used.
The concentration of enzyme substrate (aldehyde precursor) may be between 0.001 M and 6 M and preferably between 0.1 M and 4 M.
The reaction may be performed between pH 3 and pH 11 and preferably between pH 5 and pH 9.5.
The reaction temperature may be between 100C and 800C and preferably between 200C and 65°C.
The hydrazone concentration of the reaction medium is between 0.01 M and 3 M and preferably between 0.1 M and 1 M.
The content of cofactor for said enzymes may be between 0.01 mM and 1 M and preferably between 0.1 mM and 10 mM.
During the implementation of the synthesis of the compounds of formula (I), the reagents: the hydrazone(s), the enzyme(s), the substrate for said enzyme, and/or the cofactor for said enzyme, and the oxidizing agent and/or the system for regenerating the cofactor are mixed together, and the pH and the temperature are adjusted.
The compounds of formula I may also be prepared via a process in which a compound of formula (F1) or (F2)
Figure imgf000025_0001
Formula Fl Formula F2 with Z14, Z15, Z16, Ro, R24 and R25 for formula F1 and Z17, Z18, Z19, Z20, Ro, R24 and R26 for formula F2 having the meanings described above, is reacted in the presence of one equivalent of a hydrazone of formula (A) or (B).
According to one preferred variant, the compounds of formula (F1 ) or (F2) may be obtained by reacting a compound of formula R"23C(OR24)3 and a hydrazone of formula (A) or (B) in the presence or absence of a protic solvent whose boiling point ranges between 660C and 1800C. R"23 has the same meaning as R0 of formula (I) and R24 represents a radical chosen from methyl and ethyl groups.
Preferably, the reaction is performed in the presence of triethyl orthoformate and trimethyl orthoacetate at a temperature of between 0°C and 1500C for a period of between 30 minutes and 12 hours.
Preferably, the protic solvent is chosen from H2O, ethanol and methanol.
According to the invention, the term "amino silicone" means any silicone comprising at least one primary, secondary or tertiary amine or a quaternary ammonium group.
According to the invention, the amino silicones may be in the form of oils or of aqueous, alcoholic or aqueous-alcoholic solutions.
According to the invention, the amino silicones may also be in the form of oil-in-water emulsions. The oil-in-water emulsion may comprise one or more surfactants.
The surfactants may be of any nature but are preferably cationic and/or nonionic.
The number-average size of the silicone particles in the emulsion is generally between 3 nm and 500 nm, preferably between 5 nm and 300 nm, more particularly between 10 nm and 275 nm and even more preferentially between 150 and 275 nm.
The amino silicones may be chosen especially from the following compounds: (a) amino silicones corresponding to the formula:
RaG3-a-Si(OSiG2)n-(OSiGbR'2_b)m-O-SiG3-a-R'a (Vl) in which:
G is a hydrogen atom or a phenyl, OH or Ci-C8 alkyl, for example methyl, group, a denotes the number 0 or an integer from 1 to 3, in particular 0, b denotes 0 or 1 , and in particular 1 , m and n are numbers such that the sum (n + m) can range especially from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and in particular from 49 to 149 and m possibly denoting a number from 1 to 2000, and in particular from 1 to 10; R' is a monovalent radical of formula -CqH2qL in which q is a number from 2 to 8 and
L is an optionally quaternized amine group chosen from the groups: -NR"-CH2-CH2-N'(R")2 -N(R")2 -NΦ(R")3A- -NH®(R")2A-
-NH2 Θ(R")A"
-N(R")-CH2-CH2-N®R"H2A-, in which R" can denote hydrogen, phenyl, benzyl or a saturated monovalent hydrocarbon- based radical, for example an alkyl radical containing from 1 to 20 carbon atoms, and A" represents a halide ion such as, for example, fluoride, chloride, bromide or iodide.
When G denotes OH or a methyl radical and when CqH2q represents a propyl, isopropyl or isobutyl radical and L represents an amino group of formula NH-CH2-CH2-NH2, the amino silicones of formula (Vl) are known as Amodimethicones according to the classification in the "International Cosmetic Ingredient Dictionary and Handbook" 9th edition, 2002.
Among the compounds for which some of the substituents G denote OH, mention may be made in particular of those of formula (VII) below:
Figure imgf000026_0001
in which n' + n" is equal to n+1 , n and m corresponding to the definitions given for the compounds of formula (Vl). It is thus possible to use, for example, the product sold under the name "Cationic Emulsion DC 939" by the company Dow Corning, which comprises, besides amodimethicone, a cationic surfactant trimethylcetylammonium chloride in combination with a nonionic surfactant Trideceth-12.
Another product corresponding to the compounds of formula (Vl) is the silicone known as "trimethylsilylamodimethicone", corresponding to formula (VIII):
(CH3),
Figure imgf000027_0001
in which n and m have the meanings given for formula (Vl).
Such polymers are described, for example, in patent application EP-A-95238.
Another commercial product of this family that may be used according to the invention is the product sold under the name "Dow Corning Q2 7224" by the company Dow Corning, comprising, in combination, the trimethylsilylamodimethicone of formula (X), a nonionic surfactant of formula: C18H17-C6H4-(OCH2CH2)n-CιH in which n = 40, also known as octoxynol-40, and another nonionic surfactant of formula: C12H25-(OCH2CH2)n-OH in which n = 6, also known as isolaureth-6, and glycol.
Another product corresponding to this definition is an amino silicone of formula (IX) below:
Figure imgf000027_0002
in which: m and n are numbers such that the sum (n + m) may range especially from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and especially from 49 to 149, and m possibly denoting a number from 1 to 2000 and especially from 1 to 10; A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.
The weight-average molecular mass of the amino silicones preferably ranges from 2000 to 1 000 000 and even more particularly from 3500 to 200 000.
According to the invention, the viscosity at 250C of the amino silicone is especially greater than 25 000 cSt (mm2/s) and preferably ranges from 30 000 to 200 000 cSt (mm2/s) and more particularly from 30 000 to 150 000 cSt (mm2/s).
These amino silicones preferably have an amine number of less than or equal to 0.4 meq./g, preferably ranging from 0.001 to 0.2 meq./g and more particularly ranging from 0.01 to 0.1 meq./g.
The amine number is the number of milli-equivalents of amine per gram of compound. This number is determined in an entirely conventional manner via titration methods with coloured indicator or via potentiometric titration.
A silicone corresponding to this formula is, for example, DC2-8299 from Dow Corning, sold in the form of a cationic emulsion.
(b) amino silicones corresponding to formula (X):
Figure imgf000028_0001
(X) in which:
Rs represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a Ci-C18 alkyl or C2-Ci8 alkenyl radical, for example methyl;
Re represents a divalent hydrocarbon-based radical, in particular a Ci-Ci8 alkylene radical or a divalent CrCi8, for example C1-C8, alkyleneoxy radical linked to the Si via an SiC bond;
Q" is an anion such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.); r represents an average statistical value from 2 to 20 and in particular from 2 to 8; s represents an average statistical value from 20 to 200 and in particular from 20 to 50. Such amino silicones are described more particularly in patent US 4 185 087.
A silicone falling within this category is the silicone sold in the form of a cationic emulsion by the company Union Carbide under the name "Ucar Silicone ALE 56".
(c) quaternary ammonium silicones of formula (Xl):
Figure imgf000029_0001
(Xl) in which: R7, which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a ring containing 5 or 6 carbon atoms, for example methyl;
R6 represents a divalent hydrocarbon-based radical, in particular a C1-Ci8 alkylene radical or a divalent C1-C18, for example C1-C8, alkyleneoxy radical linked to the Si via an SiC bond;
R8, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a radical -R6-NHCOR7;
X- is an anion such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.); r represents an average statistical value from 2 to 200 and in particular from 5 to 100.
These silicones are described, for example, in application EP-A-O 530 974.
Silicones falling within this category are the silicones sold in solution in propylene glycol by the company Goldschmidt under the names Abil® Quat 3270, Abil® Quat 3272 and Abil® Quat 3474.
(d) the amino silicones of formula (XII):
Figure imgf000030_0001
in which:
- R1, R2, R3 and R4, which may be identical or different, denote a C1-C4 alkyl radical or a phenyl group, - R5 denotes a C1-C4 alkyl radical or a hydroxyl group,
- n is an integer ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and in which x is chosen such that the amine number is between 0.01 and 1 meq./g.
(e) amino silicones containing alkoxy groups
These amino silicones are preferably of formula (XIII) or (XIV):
R,-
Figure imgf000030_0002
in which: m and n are numbers such that the sum (n + m) can range especially from 1 to 1000, in particular from 50 to 250 and more particularly from 100 to 200, n possibly denoting a number from 0 to 999, especially from 49 to 249 and more particularly from 125 to 175 and m possibly denoting a number from 1 to 1000, especially from 1 to 10 and more particularly from 1 to 5;
R1, R2 and R3, which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 to R3 denoting an alkoxy radical.
Preferably, the alkoxy radical is a methoxy radical.
The hydroxyl/alkoxy mole ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and is more particularly equal to 0.3.
The amino silicone of formula (XIII) has a weight-average molecular mass preferably ranging from 2000 to 1 000 000 and even more particularly from 3500 to 200 000;
CH, CH, CH, H,
R; Si- O — Si- O — Si - -Q gj JD
(CH2)3
CH, CH, CH,
NH (CH2)2
NH.
(XIV) in which: p and q are numbers such that the sum (p + q) can range especially from 1 to 1000, in particular from 50 to 350 and more particularly from 150 to 250, p possibly denoting a number from 0 to 999, especially from 49 to 349 and more particularly from 159 to 239, and q possibly denoting a number from 1 to 1000, especially from 1 to 10 and more particularly from 1 to 5;
R1 and R2, which are different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 and R2 denoting an alkoxy radical.
Preferably, the alkoxy radical is a methoxy radical.
The hydroxyl/alkoxy mole ratio preferably ranges from 1 :0.8 to 1 :1.1 and preferably from 1 :0,9 to 1 :1 and is more particularly equal to 1 :0.95.
The amino silicone of formula (XIV) has a weight-average molecular mass preferably ranging from 2000 to 200 000, more particularly from 5000 to 100 000 and more particularly from 10 000 to 50 000.
The commercial products corresponding to these silicones of structure (XIII) or (XIV) may include in their composition one or more other amino silicones whose structure is different from structures (XIII) and (XIV).
A product containing amino silicones of structure (XIII) is sold by the company Wacker under the name Belsil® ADM 652.
A product containing amino silicones of structure (XIV) is sold by the company Wacker under the name Fluid WR 1300®.
The amino silicone microemulsions of formula (XIV) sold under the names Finish CT 96 E® or SLM 28020® by the company Wacker may also be used.
The weight-average molecular masses of all these amino silicones are measured by gel permeation chromatography (GPC) at room temperature, as polystyrene equivalents. The columns used are μ styragel columns. The eluent is THF and the flow rate is 1 ml/minute. 200 μl of a solution containing 0.5% by weight of silicone in THF are injected. Detection is performed by refractometry and UV-metry.
The silicones that are particularly preferred in accordance with the invention are:
- polysiloxanes containing amine groups, such as amodimethicones, including trimethylsilyl- amodimethicones.
According to the invention, the amino silicone(s) may represent from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight and more particularly from 0.1% to 3% by weight relative to the total weight of the final composition.
The suitable dyeing medium (or support) generally consists of water or of a mixture of water and of at least one organic solvent to dissolve the compounds that are not sufficiently water- soluble. Examples of organic solvents that may be mentioned include C1-C4 lower alkanols, such as ethanol and isopropanol; aromatic alcohols, for instance benzyl alcohol, and also similar products and mixtures thereof.
The solvents may be present in proportions preferably between 1% and 40% by weight approximately and even more preferentially between 5% and 30% by weight approximately relative to the total weight of the dye composition.
The pH of the dye composition in accordance with the invention is generally between 2 and
11 approximately and preferably between 5 and 10 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres.
Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids. Among the 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 (XV) below:
Figure imgf000033_0001
in which w is a propylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom or a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
In addition to the cationic direct dye(s) (i) defined above, the dye composition in accordance with the invention may contain one or more additional direct dyes that may be chosen, for example, from nitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, xanthene dyes and non-cationic azo dyes.
When it is intended for oxidation dyeing, the dye composition in accordance with the invention contains, in addition to the cationic direct dye(s) (i), one or more oxidation bases chosen from the oxidation bases conventionally used for oxidation dyeing, and among which mention may be made especially of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among these oxidation bases, mention may be made most particularly of:
- (I) the para-phenylenediamines of formula (XVI) below, and the addition salts thereof with an acid:
Figure imgf000033_0002
in which:
R-I represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a (C1-C4)alkoxy(C1-C4)alkyl radical, a C1-C4 alkyl radical substituted with a nitrogenous group, a phenyl group or a 4'-aminophenyl group;
R2 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a (C1-C4)alkoxy(C1-C4)alkyl radical or a C1-C4 alkyl radical substituted with a nitrogenous group; R1 and R2 may also form with the nitrogen atom that bears them a 5- or 6-membered nitrogenous heterocycle optionally substituted with one or more alkyl, hydroxy or ureido groups;
R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a Ci-C4 alkyl radical, a sulfo radical, a carboxy radical, a Ci-C4 monohydroxyalkyl radical, a Ci-C4 hydroxyalkoxy radical, an acetylamino(Ci-C4)alkoxy radical, a CrC4 mesylaminoalkoxy radical or a carbamoylamino(Ci-C4)alkoxy radical,
R4 represents a hydrogen or halogen atom or a CrC4 alkyl radical.
Among the nitrogenous groups of formula (XVI) above, mention may be made in particular of amino, mono(Ci-C4)alkylamino, di(Ci-C4)alkylamino, tri(CrC4)alkylamino, monohydroxy(Ci- C4)alkylamino, imidazolinium and ammonium radicals.
Examples of para-phenylenediamines of formula (XVI) above that may especially be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylene diamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N1N- dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para- phenylenediamine, 4-amino-N,N-bis(β-hydroxyethyl)-2-methylaniline, 4-amino-2-chloro-N,N- bis(β-hydroxyethyl)aniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para- phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para- phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para- phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxy propyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para- phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy- para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 2-methyl-1-N-β- hydroxyethyl-para-phenylenediamine, and the addition salts thereof with an acid.
Among the para-phenylenediamines of formula (XVI) above, para-phenylenediamine, para- tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylene- diamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxy- ethyl)-para-phenylenediamine and 2-chloro-para-phenylenediamine, and the addition salts thereof with an acid are most particularly preferred.
- (II) According to the invention, the term double bases is understood to refer to the compounds containing at least two aromatic nucleii bearing amino and/or hydroxyl groups. Among the double bases that may be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made in particular of the compounds corresponding to formula (XVII) below, and the addition salts thereof with an acid:
Figure imgf000035_0001
in which
- Z1 and Z2, which may be identical or different, represent a hydroxyl or -NH2 group that may be substituted with a Ci-C4 alkyl radical or with a linker arm Y;
- the linker arm Y represents a linear or branched alkylene chain containing from 1 to 14 carbon atoms, which may be interrupted by or terminated with one or more nitrogenous groups and/or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and optionally substituted with one or more hydroxyl or C1-C6 alkoxy radicals;
- R5 and R6 represent a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a C1-C4 aminoalkyl radical or a linker arm Y;
- R7, R8, Rg, Rio> Rn and Ri2, which may be identical or different, represent a hydrogen atom, a linker arm Y or a C1-C4 alkyl radical; it being understood that the compounds of formula (XVII) contain only one linker arm Y per molecule.
Among the nitrogenous groups of formula (XVII) above, mention may be made in particular of amino, mono(CrC4)alkylamino, di(CrC4)alkylamino, tri(CrC4)alkylamino, monohydroxy(Ci-C4)alkylamino, imidazolinium and ammonium radicals.
Among the double bases of formula (XVII) above, mention may be made more particularly of
N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol, N,N'-bis(β-hydroxy ethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylene diamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis (4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine and 1 ,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition salts thereof with an acid.
Among these double bases of formula (XVII), N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-amino- phenyl)-1 ,3-diaminopropanol and 1 ,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or one of the addition salts thereof with an acid, are particularly preferred.
- (Ill) para-Aminophenols that may especially be mentioned include those corresponding to formula (XVIII) below, and the addition salts thereof with an acid:
Figure imgf000036_0001
(XVIII) in which:
R13 represents a hydrogen atom, a halogen atom such as fluorine, a Ci-C4 alkyl, C1-C4 monohydroxyalkyl, (C1-C4)alkoxy(C1-C4)alkyl, C1-C4 aminoalkyl or hydroxy(C1-C4)alkylamino(C1-C4)alkyl radical,
Ri4 represents a hydrogen atom or a halogen atom such as fluorine, a Ci-C4-alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl, Ci-C4 cyanoalkyl or (C1-C4)alkoxy(C1-C4)alkyl radical.
Among the para-aminophenols of formula (XVIII) above, mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino- 3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino- 2-methoxymethylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-
(β-hydroxyethylaminomethyl)phenol, and the addition salts thereof with an acid.
- (IV) The ortho-aminophenols that may be used as oxidation bases in the context of the present invention are chosen especially from 2-aminophenol, 2-amino-1-hydroxy-5- methylbenzene, 2-amino-1-hydroxy-6-methylbenzene and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
- (V) Among the heterocyclic bases that may be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made more particularly of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and the addition salts thereof with an acid.
Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxy pyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine, and the addition salts thereof with an acid.
Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine and 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made especially of pyrazolo[1 ,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1 ,5-a] pyrimidine-3,7-diamine; pyrazolo[1 ,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1 ,5-a] pyrimidine-3,5-diamine; 3-aminopyrazolo[1 ,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1 ,5-a] pyrimidin-5-ol; 2-(3-aminopyrazolo[1 ,5-a]pyrimidin-7-ylamino)ethanol; 2-(7-aminopyrazolo- [1 ,5-a]-pyrimidin-3-ylamino)ethanol; 2-[(3-aminopyrazolo-[1 ,5-a]pyrimidin-7-yl)(2-hydroxy ethyl)amino]-ethanol; 2-[(7-aminopyrazolo[1 ,5-a]pyrimidin-3-yl)(2-hydroxy-ethyl) amino] ethanol; 5,6-dimethylpyrazolo[1 ,5-a]pyrimidine-3,7-diamine; 2,6-dimethylpyrazolo[1 ,5-a]- pyrimidine-3,7-diamine; 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and 3- amino-5-methyl-7-imidazolylpropylaminopyrazolo[1 ,5-a]pyrimidine and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists, and the addition salts thereof with an acid.
Among the pyrazole derivatives, mention may be made more particularly of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 -(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3-dimethyl- pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, A- amino-1 ,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5- diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5- diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 4,5- diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5- diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl- 3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β- hydroxyethyl)amino-1-methylpyrazole, and the addition salts thereof with an acid.
When they are used, the oxidation base(s) preferably represent(s) from 0.0005% to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005% to 6% by weight approximately relative to this weight. When it is intended for oxidation dyeing, the dye composition in accordance with the invention may also contain, in addition to the cationic direct dye (i) and the amino silicone (ii) and also oxidation bases, one or more couplers so as to modify or to enrich with tints the shades obtained using the cationic direct dye(s) (i) and the oxidation base(s).
The couplers that may be used in the dye composition according to the invention are those conventionally used in oxidation dye compositions, i.e. meta-aminophenols, meta- phenylenediamines, meta-diphenols, naphthols and heterocyclic couplers, for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3-benzodioxoles, quinolines and the addition salts thereof with an acid.
These couplers are more particularly chosen from 2,4-diamino-1-(β- hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methyl- phenol, 3-aminophenol, 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 4-chloro- 1 ,3-dihydroxybenzene, 2-amino-4-(β-hydroxyethylamino)-1 -methoxybenzene, 1 ,3- diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, sesamol, 1-amino-2-methoxy-4,5- methylenedioxybenzene α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methyl- indole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1 H-3-methylpyrazol-5-one, 1- phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-1 ,2,4- triazole, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, and the addition salts thereof with an acid.
In general, the addition salts with an acid of the oxidation bases and couplers are especially chosen from the hydrochlorides, hydrobromides, sulfates, tartrates, lactates and acetates.
When they are present, the coupler(s) preferably represent(s) from 0.0001% to 10% by weight approximately relative to the total weight of the dye composition, and even more preferentially from 0.005% to 5% by weight approximately relative to this weight.
The dye composition in accordance with the invention may also contain various adjuvants conventionally used in hair dye compositions, such as antioxidants, penetrants, sequestrants, fragrances, buffers, nonionic, anionic or amphoteric polymers, non-silicone cationic polymers, nonionic, cationic or amphoteric surfactants, ceramides, preserving agents, screening agents and opacifiers.
Needless to say, a person skilled in the art will take care to select the optional additional compound(s) such that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The dye composition according to the invention may be in various forms, such as in the form of liquids, shampoos, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair. It may be obtained by extemporaneously mixing a composition, optionally a pulverulent composition, containing the cationic direct dye(s) with a composition containing at least one oxidation base and at least one amino silicone.
When the combination of the cationic direct dye (i) and of the amino silicone (ii) according to the invention is used in a composition for oxidation dyeing (one or more oxidation bases are then used, optionally in the presence of one or more couplers) or when it is used in a composition for lightening direct dyeing, then the dye composition in accordance with the invention also contains at least one oxidizing agent chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases, laccases and two-electron oxidoreductases. The use of hydrogen peroxide or of enzymes is particularly preferred.
Another subject of the invention is a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.
According to a first variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibres for a time that is sufficient to develop the desired coloration, after which the fibres are rinsed, optionally washed with shampoo, rinsed again and dried.
The time required to develop the coloration on the keratin fibres is generally between 3 and 60 minutes and even more precisely between 5 and 40 minutes.
According to a second variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibres for a time that is sufficient to develop the desired coloration, without final rinsing.
According to another particular embodiment of this dyeing process, and when the dye composition in accordance with the invention contains at least one oxidizing agent, the dyeing process comprises a preliminary step that consists in separately storing, on the one hand, a composition (A1) comprising, in a suitable dyeing medium, at least one cationic direct dye (i) as defined above and, on the other hand, a composition (B1 ) containing, in a suitable dyeing medium, at least one oxidizing agent, and then in mixing them together at the time of use, followed by applying this mixture to the keratin fibres, composition (A1 ) or composition (B1) containing at least one amino silicone as defined above.
According to another particular embodiment of this dyeing process, and when the dye composition in accordance with the invention contains at least one oxidation base and at least one oxidizing agent, the dyeing process includes a preliminary step that consists in separately storing, on the one hand, a composition (A2) comprising, in a suitable dyeing medium, at least one cationic direct dye (i) as defined above and at least one oxidation base, and, on the other hand, a composition (B2) containing, in a suitable dyeing medium, at least one oxidizing agent, and then in mixing them together at the time of use, followed by applying this mixture to the keratin fibres, composition (A2) or composition (B2) containing at least one amino silicone (ii) as defined above.
Another subject of the invention is a multi-compartment device or dyeing "kit" or any other multi-compartment packaging system, of which a first compartment contains composition (A1) or (A2) as defined above, and a second compartment contains composition (B1) or (B2) as defined above. These devices may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR 2 586 913 in the name of the Applicant.
The examples that follow are intended to illustrate the invention without, however, limiting its scope. EXAMPLES
Figure imgf000040_0001
Application Examples Example 1
The dye composition below was prepared (amounts expressed as grams of active material):
Figure imgf000041_0001
The composition was applied firstly to locks of natural grey hair containing 90% white hairs, and secondly to locks of permanent-waved grey hair containing 90% white hairs, for 30 minutes at room temperature (2O0C).
After the action time, the locks are rinsed, shampooed and then rinsed and dried. They are dyed in a sparingly selective very chromatic violet-blue shade.
Example 2
A similar result to that of Example 1 is obtained by replacing dye 1 weight for weight with dye 2 and the amino silicone emulsion Dow Corning 8299 with the amino silicone SLM 28020® sold by the company Wacker.

Claims

1. Composition for dyeing keratin fibres, in particular human keratin fibres and more particularly the hair, comprising, in a suitable dyeing medium, at least one amino silicone and at least one tetraazapentamethine compound of formula I
Figure imgf000042_0001
in which
W1 represents a cationic heteroaromatic radical of formula (II) or
Figure imgf000042_0002
W2 represents a heteroaromatic radical of formula (IV) or (V):
Figure imgf000042_0003
in which:
Z0 represents a radical CR2, a nitrogen atom or a radical NR21,
Z1 represents an oxygen or sulfur atom or a radical NR9,
Z2 represents a nitrogen atom or a radical CRi0, - Z3 represents a nitrogen atom or a radical CRi1,
Z4 represents a nitrogen atom or a radical CR12,
Z5 represents a nitrogen atom or a radical CR13,
Z6 represents a nitrogen atom or a radical CR14,
Z7 represents an oxygen or sulfur atom or a radical NR15, - Z8 represents a nitrogen atom or a radical CR16,
Zg represents a nitrogen atom or a radical CR17,
Z10 represents a nitrogen atom or a radical CRi8,
Z-I 1 represents a nitrogen atom or a radical CRi9,
Z12 represents a nitrogen atom or a radical CR20, - Zi3 represents a radical CR6, a nitrogen atom or a radical NR22, it being understood that each of the rings of formulae (II), (III), (IV) and (V)
1 comprise not more than three nitrogen atoms and that two of the three nitrogen atoms may be contiguous, the bond a of the 5-membered cationic heteroaromatic radical of formula
(II) being linked to the nitrogen atom Ni of formula (I), the bond b of the 6-membered cationic heteroaromatic radical of formula
(III) being linked to the nitrogen atom Ni of formula (I), the double bond a' of the 5-membered heteroaromatic radical of formula
(IV) being linked to the nitrogen atom N2 of formula (I), the double bond b' of the 6-membered heteroaromatic radical of formula (V) being linked to the nitrogen atom N2 of formula (I), the bond b, linking the cationic heteroaromatic radical of formula (III) to the nitrogen atom N-i of formula (I), being in an ortho or para position relative to the nitrogen atom bearing the radical R4 when Z5 represents a radical CR13; the bond b being in an ortho position relative to the nitrogen atom bearing the radical R4 when Z5 represents a nitrogen atom, the bond b', linking the heteroaromatic radical of formula (V) to the nitrogen atom N2 of formula (I), being in an ortho or para position relative to the nitrogen atom bearing the radical R7 when Z11 represents a radical CR-ig; the bond b' being in an ortho position relative to the nitrogen atom bearing the radical R7 when Z-n represents a nitrogen atom,
R2, R6, R10 and R16 represent, independently of each other, a hydrogen atom; a linear or branched C1-C4 alkyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino and C1-C2 (di)alkylamino radicals; a carboxyl radical; a sulfonylamino radical, R1, R4, R5, R7, Rg, Ri5, R21 and R22 represent, independently of each other, a linear or branched C1-C8 alkyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals;
R0, R3, Rs, Rii. Ri2> Ri3> Ri4> Ri7, Ri8. Ri9 and R20 represent, independently of each other, a hydrogen atom, a linear or branched C1-C16 hydrocarbon-based chain, this chain possibly being saturated or unsaturated with one to three unsaturations, this chain being unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl, sulfonic, sulfonylamino and C2-C4 (poly)hydroxyalkylamino radicals or a halogen atom such as chlorine, fluorine or bromine; a phenyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 5 (di)alkylamino, carboxyl, sulfonic, sulfonylamino and C2-C4 (poly)hydroxy- alkylamino radicals or a halogen atom such as chlorine, fluorine or bromine; a heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl and pyridazinyl radicals; in addition, this hydrocarbon-based chain may be o interrupted with one or two oxygen, nitrogen or sulfur atoms or with an SO2 radical, it being understood that R0, R3, R8, Rn, R12, R13, R14, R17, R-is, R19 and R20 do not comprise a peroxide bond or diazo or nitroso radicals, R2 with R10, R11 with Ri2, R6 with R16, and R17 with R18 can form, 5 independently of each other, a 5- or 6-membered carbon-based aromatic ring, which is unsubstituted or substituted with one or two hydroxyl, amino, (di)(C1-C2)alkylamino, C1-C2 alkoxy or C2-C4 (poly)hydroxyalkylamino radicals, X is an organic or mineral anion. 0
2. Composition according to Claim 1 , characterized in that, in formula I, Z1 represents an oxygen atom or a radical NR9 and Z7 represents an oxygen atom or a radical NR15.
3. Composition according to Claims 1 and 2, in which R0 represents a hydrogen atom; a linear or branched C1-C6 alkyl radical, which is unsubstituted or 5 substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4
(poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, C2-C4 (poly)hydroxyalkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one to three radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals or 0 a halogen atom such as chlorine, fluorine or bromine; an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl and pyridazinyl radicals.
4. Composition according to any one of the preceding claims, in which R0 represents a hydrogen atom; a methyl, ethyl or 2-methoxyethyl radical; a phenyl 5 radical, which is unsubstituted or substituted with an amino, (di)methylamino or (di)(2-hydroxyethyl)amino radical, or an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl and pyridyl radicals.
5. Composition according to any one of the preceding claims, in which R2, R6, R10 and Ri6 represent a hydrogen atom, a C1-C4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, CrC2 (di)alkylamino and carboxyl radicals, or a phenyl radical.
6. Composition according to any one of the preceding claims, in which R2, R6, Rio and Ri6 preferably represent a hydrogen atom, a methyl, phenyl or 2- hydroxymethyl radical or a carboxyl.
7. Composition according to any one of the preceding claims, in which R-i, R4, R5, R7, R9, R15, R21 and R22 preferably represent a C1-C4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C1-C2 alkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals.
8. Composition according to any one of the preceding claims, in which R1, R4, R5, R7, R9, R15, R2-I and R22 represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxy- methyl, 2-carboxyethyl or 2-sulfonylethyl radical.
9. Composition according to any one of the preceding claims, in which R3, R8, R11, R12, R13, R14, R17, R18, Rig and R20 represent, independently of each other, a hydrogen atom; a linear or branched C1-C4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, carboxyl and sulfonic radicals or a halogen atom such as chlorine, fluorine or bromine; a sulfonylamino radical; a C2-C4 (poly)hydroxyalkylamino radical.
10. Composition according to any one of the preceding claims, in which R3, R8, R11, R12, R13, Ri4, R17, R-I8, R19 and R20 represent, independently of each other, a hydrogen atom, a methyl or 2-hydroxymethyl radical, a carboxyl, a methoxy, ethoxy or 2-hydroxyethyloxy radical, or an amino, methylamino, dimethylamino or 2-hydroxyethylamino radical.
11. Composition according to any one of the preceding claims, in which W1 is a 2-pyridinium radical and W2 is a 2-pyridine radical.
12. Composition according to Claim 11 , in which the compound of formula (I) is chosen from the following compounds:
- 2-[5-(N-methyl-2-pyridinylidene)-1-formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-methyl-1-formazano]-N-methylpyridinium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-ethyl-1 -formazano]-N-methy!pyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-isopropyl-1-formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-phenyl-1-formazano]-N-methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- methylpyridinium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- N-methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-1-formazano]-4-pyrrolidino-N- methylpyridinium chloride - 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-methyl-1 -formazano]-4- pyrrolidino-N-methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-ethyl-1-formazano]-4- pyrrolidino-N-methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-isopropyl-1-formazano]-4- pyrrolidino-N-methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-phenyl-1-formazano]-4- pyrrolidino-N-methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1- formazano]-4-pyrrolidino-N-methylpyridinium chloride - 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1- formazano]-4-pyrrolidino-N-methylpyridinium chloride
- 2-[5-(4-pyrrolidino-N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)- 1 -formazano]-4-pyrrolidino-N-methylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-1-formazano]-N-hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-methyl-1 -formazano]-N- hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-ethyl-1-formazano]-N- hydroxyethylpyridinium chloride - 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-phenyl-1 -formazano]-N- hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-N- hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- hydroxyethylpyridinium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1 - formazano]-N-hydroxyethylpyridinium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-1-formazano]-N-carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-methyl-1-formazano]-N- carboxyethylpyridinium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-ethyl-1-formazano]-N- carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-phenyl-1-formazano]-N- carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-isopropyl-1-formazano]-N- carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- carboxyethylpyridinium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- carboxyethylpyridinium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1 - formazano]-N-carboxyethylpyridinium chloride.
13. Composition according to any one of Claims 1 to 10, in which W1 is a 4- pyridinium radical and W2 is a 4-pyridine radical.
14. Composition according to Claim 13, in which the compound of formula (I) is chosen from the following compounds:
- 4-[5-(N-methyl-4-pyridinylidene)-1 -formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-methyl-1-formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-ethyl-1-formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-isopropyl-1-formazano]-N-methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-phenyl-1-formazano]-N-methylpyridinium chloride - 4-[5-(N-methyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-N- methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- methylpyridinium chloride
- 4-[5-(N-methyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- N-methylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-1 -formazano]-N-hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-methyl-1 -formazano]-N- hydroxyethylpyridinium chloride - 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-ethyl-1-formazano]-N- hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-N- hydroxyethylpyridinium chloride - 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-N- hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-N- hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-N- hydroxyethylpyridinium chloride
- 4-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-N-hydroxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-1-formazano]-N-carboxyethylpyridinium chloride - 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-N- carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-ethyl-1-formazano]-N- carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-N- carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-isopropyl-1-formazano]-N- carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-N- carboxyethylpyridinium chloride - 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-N- carboxyethylpyridinium chloride
- 4-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-N-carboxyethylpyridinium chloride.
15. Composition according to any one of Claims 1 to 10, in which W-i is a 2- imidazolium radical and W2 is a 2-imidazole radical.
16. Composition according to Claim 15, in which the compound of formula (I) is chosen from the following compounds:
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-1 -formazano]-1 ,3-dimethylimidazolium chloride - 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-methyl-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-ethyl-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-isopropyl-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-phenyl-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-imidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dimethylimidazolium chloride - 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-methyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazoNdene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride - 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-(4'-methoxyphenyl)-1-formazano]- 1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-(4'-hydroxyphenyl)-1-formazano]- 1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-imidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-methyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-ethyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-phenyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-isopropyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-(4'-methoxyphenyl)-1-formazano]- 1 ,3-dicarboxyethylimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-(4'-hydroxyphenyl)-1-formazano]- 1 ,3-dicarboxyethylimidazolium chloride - 2-[5-(1 ,3-dicarboxyethyl-2-imidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dicarboxyethylimidazolium chloride.
17. Composition according to any one of Claims 1 to 10, in which W1 is a 5- pyrazolium radical and W2 is a 5-pyrazole radical.
18. Composition according to Claim 17, in which the compound of formula (I) is chosen from the following compounds:
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-1-formazano]-1 ,2-dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-methyl-1-formazano]-1 ,2- dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-ethyl-1-formazano]-1 ,2- dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-isopropyl~1 -formazano]-1 ,2- dimethylpyrazolinium chloride - 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-phenyl-1-formazano]-1 ,2- dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,2- dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl-5-pyrazolidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,2- dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dimethyl~5-pyrazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,2-dimethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-1 -formazano]-1 ,2- dihydroxyethylpyrazolinium chloride - 5-[5-(1 ,2-dihydroxyethyl-5-pyrazoNdene)-3-methyl-1-formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-ethyl-1 -formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-phenyl-1 -formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-isopropyl-1 -formazano]-1 ,2- dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-(4'-methoxyphenyl)-1 -formazano]- 1 ,2-dihydroxyethylpyrazolinium chloride - 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-(4'-hydroxyphenyl)-1-formazano]- 1 ,2-dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dihydroxyethyl-5-pyrazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,2-dihydroxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-methyl-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-ethyl-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-phenyl-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-isopropyl-1 -formazano]-1 ,2- dicarboxyethylpyrazolinium chloride - 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-(4'-methoxyphenyl)-1 -formazano]- 1 ,2-dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-(4'-hydroxyphenyl)-1-formazano]- 1 ,2-dicarboxyethylpyrazolinium chloride
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-(4'-N,N-dimethylaminophenyl)-1 - formazano]-1 ,2-dicarboxyethylpyrazolinium chloride.
19. Composition according to any one of Claims 1 to 10, in which W-i is a 2- benzimidazolium radical and W2 is a 2-pyridine radical.
20. Composition according to Claim 19, in which the compound of formula (I) is chosen from the following compounds: - 2-[5-(N-methyl-2-pyridinylidene)-1 -formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-ethyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- 1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(N-hydroxyethyl-2-pyπdιnylιdene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyπdιnylιdene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(N-hydroxyethyl-2-pyπdιnylιdene)-3-ιsopropyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazohum chloride
- 2-[5-(N-hydroxyethyl-2-pyrιdιnylιdene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazohum chloride
- 2-[5-(N-hydroxyethyl-2-pyrιdιnylιdene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyπdιnylιdene)-3-(4'-N,N-dιmethylamιnophenyl)-1- formazano]-1 ,3-dιhydroxyethylbenzιmιdazolιum chloride
- 2-[5-(N-carboxyethyl-2-pyπdιnylιdene)-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyπdιnylιdene)-3-methyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyrιdιnylιdene)-3-ethyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazohum chloride
- 2-[5-(N-carboxyethyl-2-pyπdιnylιdene)-3-phenyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyπdιnylιdene)~3-ιsopropyl~1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyπdιnylιdene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazohum chloride - 2-[5-(N-carboxyethyl-2-pyπdιnylιdene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dicarboxyethylbenzimidazohum chloride
- 2-[5-(N-carboxyethyl-2-pyπdιnylιdene)-3-(4'-N,N-dιmethylamιnophenyl)-1 - formazano]-1 ,3-dιcarboxyethylbenzιmιdazolιum chloride
21 Composition according to any one of Claims 1 to 10, in which W1 is a 2- benzimidazolium radical and W2 is a 4-pyrιdιne radical
22 Composition according to Claim 21 , in which the compound of formula (I) is chosen from the following compounds
- 2-[5-(N-methyl-4-pyπdιnylιdene)-1 -formazano]-1 ,3-dιmethylbenzιmιdazolιum chloride - 2-[5-(N-methyl-4-pyπdιnylιdene)-3-methyl-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyπdιnylιdene)-3-ethyl-1-formazano]-1 ,3- dimethylbenzimidazohum chloride
- 2-[5-(N-methyl-4-pyπdιnylιdene)-3-ιsopropyl-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- 1 ,3-dimethylbenzimidazolium chloride - 2-[5-(N-hydroxyethyl-4-pyridinylidene)-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(N~hydroxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1 - formazano]-1 ,3-dihydroxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dicarboxyethylbenzimidazolium chloride.
23. Composition according to any one of Claims 1 to 10, in which W1 is a 2- imidazolium radical and W2 is a 2-pyridine radical.
24. Composition according to Claim 23, in which the compound of formula (I) is chosen from the following compounds:
- 2-[5-(N-methyl-2-pyridinylidene)-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dimethylimidazolium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-ethyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dimethylimidazolium chloride - 2-[5-(N-methyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1-formazano]- 1 ,3-dimethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-ethyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride - 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-ethyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-2-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dicarboxyethylimidazolium chloride.
25. Composition according to any one of Claims 1 to 10, in which W1 is a 2- imidazolium radical and W2 is a 4-pyridine radical.
26. Composition according to Claim 25, in which the compound of formula (I) is chosen from the following compounds:
- 2-[5-(N-methyl-4-pyridinylidene)-1-formazano]-1 ,3-dimethylimidazolium chloride - 2-[5-(N-methyl-4-pyridinylidene)-3-methyl-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-ethyl-1-formazano]-1 ,3-dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3~isopropyl-1 -formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-phenyl-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dimethylimidazolium chloride - 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dimethylimidazolium chloride
- 2-[5-(N-methyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1 -formazano]- 1 ,3-dimethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride - 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dihydroxyethylimidazolium chloride - 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1-formazano]-1 ,3- dihydroxyethylimidazolium chloride
- 2-[5-(N-hydroxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dihydroxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-methyl-1-formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-ethyl-1 -formazano]-1 ,3- dicarboxyethylirnidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-phenyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-t5-(N-carboxyethyl-4-pyridinylidene)-3-isopropyl-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-methoxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride
- 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-hydroxyphenyl)-1 -formazano]-1 ,3- dicarboxyethylimidazolium chloride - 2-[5-(N-carboxyethyl-4-pyridinylidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dicarboxyethylimidazolium chloride.
27. Composition according to any one of Claims 1 to 10, in which W1 is a 2- benzimidazolium radical and W2 is a 2-benzimidazole radical.
28. Composition according to Claim 27, in which the compound of formula (I) is chosen from the following compounds:
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-1 -formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-methyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride - 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-ethyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-isopropyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-phenyl-1-formazano]-1 ,3- dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-(4'-methoxyphenyl)-1-formazano]- 1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-(4'-hydroxyphenyl)-1-formazano]- 1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dimethyl-2-benzimidazolidene)-3-(4'-N,N-dimethylaminophenyl)-1- formazano]-1 ,3-dimethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride - 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-methyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-ethyl-1 -formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-phenyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-isopropyl-1-formazano]-1 ,3- dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-(4'-methoxyphenyl)-1- formazano]-1 ,3-dihydroxyethylbenzimidazolium chloride - 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-(4'-hydroxyphenyl)-1- formazano]-1 ,3-dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dihydroxyethyl-2-benzimidazolidene)-3-(4'-N,N-dimethylamino phenyl)-1-formazano]-1 ,3-dihydroxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-methyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-ethyl-1 -formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride - 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-phenyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-isopropyl-1-formazano]-1 ,3- dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-(4'-methoxyphenyl)-1 - formazano]-1 ,3-dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-(4'-hydroxyphenyl)-1 - formazano]-1 ,3-dicarboxyethylbenzimidazolium chloride
- 2-[5-(1 ,3-dicarboxyethyl-2-benzimidazolidene)-3-(4'-N,N- dimethylaminophenyl)-1-formazano]-1 ,3-dicarboxyethylbenzimidazolium chloride.
29. Composition according to any one of the preceding claims, characterized in that the compound(s) of formula I is (are) present in a concentration ranging from 0.001 % to 5% and preferably from 0.05% to 2% by weight relative to the total weight of the composition.
30. Composition according to any one of the preceding claims, characterized in that the amino silicone is chosen from the amino silicones corresponding to the formula:
RaG3-a-Si(OSiG2)n-(OSiGbR'2.b)m-O-SiG3.a-R'a (Vl) in which:
G is a hydrogen atom or a phenyl, OH or CrC8 alky], for example methyl, group, a denotes the number 0 or an integer from 1 to 3, in particular 0, b denotes 0 or 1 , and in particular 1 , m and n are numbers such that the sum (n + m) can range especially from
1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and in particular from 49 to 149 and m possibly denoting a number from 1 to 2000, and in particular from 1 to 10;
R' is a monovalent radical of formula -CqH2qL in which q is a number from 2 to 8 and L is an optionally quaternized amine group chosen from the groups:
-NR"-CH2-CH2-N'(R")2
-N(FT)2
-NΘ(R")3A-
-NHΘ(R")2A~ -NH2 Θ(R")A-
-N(R")-CH2-CH2-NΘRΗ2A", in which R" can denote hydrogen, phenyl, benzyl or a saturated monovalent hydrocarbon-based radical, for example an alkyl radical containing from 1 to 20 carbon atoms, and A" represents a halide ion such as, for example, fluoride, chloride, bromide or iodide.
31. Composition according to the preceding claim, characterized in that the amino silicone is chosen from the silicones corresponding to formula (VII):
Figure imgf000059_0001
in which n' + n" is equal to n+1.
32 Composition according to Claim 30, characterized in that the amino silicone is chosen from the silicones corresponding to formula (VIII)
(CHA
Figure imgf000059_0002
33 Composition according to Claim 30, characterized in that the amino silicone is chosen from the compounds of formula (IX) below.
CH3 CH, CH,
HO- -Si — O- - Sr O — Sr -O — Si — OH I A
CH, CH, CH,
NH (CH2)2
NH,
(IX) in which. m and n are numbers such that the sum (n + m) may range especially from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to
1999 and especially from 49 to 149, and m possibly denoting a number from 1 to
2000 and especially from 1 to 10,
A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms, which is preferably linear
34. Composition according to any one of the preceding claims, characterized in that the amino silicone is chosen from the amino silicones corresponding to formula (X)
Figure imgf000060_0001
(X) in which:
R5 represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a CrC18 alkyl or C2-C18 alkenyl radical, for example methyl;
R6 represents a divalent hydrocarbon-based radical, in particular a C1-C18 alkylene radical or a divalent C1-C18, for example C1-C8, alkyleneoxy radical linked to the Si via an SiC bond;
Q" is an anion such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc.); r represents an average statistical value from 2 to 20 and in particular from 2 to 8; s represents an average statistical value from 20 to 200 and in particular from 20 to 50.
35. Composition according to any one of the preceding claims, characterized in that the amino silicone is chosen from the quaternary ammonium silicones of formula (Xl):
2,- 7 N,:- R
Figure imgf000060_0002
(Xl) in which:
R7, which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a ring containing 5 or 6 carbon atoms, for example methyl;
R6 represents a divalent hydrocarbon-based radical, in particular a C1-C18 alkylene radical or a divalent C1-Ci8, for example Ci-C8, alkyleneoxy radical linked to the Si via an SiC bond;
R8, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a radical -R6- NHCOR7; X- is an anion such as a halide ion, in particular chloride, or an organic acid salt (acetate, etc ), r represents an average statistical value from 2 to 200 and in particular from 5 to 100
36. Composition according to any one of the preceding claims, characterized in that the amino silicone is chosen from the amino silicones of formula (XII).
Figure imgf000061_0001
NH,
(XII) in which
- R1, R2, R3 and R4, which may be identical or different, denote a C1-C4 alkyl radical or a phenyl group,
- R5 denotes a C1-C4 alkyl radical or a hydroxyl group,
- n is an integer ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and in which x is chosen such that the amine number is between 0.01 and 1 meq./g.
37 Composition according to any one of the preceding claims, characterized in that the amino silicone is chosen from amino silicones containing alkoxy groups
38. Composition according to the preceding claim, characterized in that the ammo silicone is chosen from the amino silicones of formula (XIII).
CH, CH, CH,
R1 Si O — Si O — Si - -O — Si — R,
(CH2)3
CH, CH, CH,
NH
(CH2J2
NH, m (XIII) in which m and n are numbers such that the sum (n + m) can range especially from 1 to
1000, in particular from 50 to 250 and more particularly from 100 to 200, n possibly denoting a number from 0 to 999, especially from 49 to 249 and more particularly from 125 to 175 and m possibly denoting a number from 1 to 1000, especially from 1 to 10 and more particularly from 1 to 5, R1, R2 and R3, which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 to R3 denoting an alkoxy radical
39 Composition according to the preceding claim, characterized in that the alkoxy radical is a methoxy radical
40 Composition according to the preceding claim, characterized in that the hydroxyl/alkoxy mole ratio is preferably between 0 2 1 and 0 4 1 , preferably between 0 25 1 and 0 35 1 and is more particularly equal to 0 3
41 Composition according to Claim 37, characterized in that the amino silicone is chosen from the amino silicones of formula (XIV)
CH, CH, CH, CH,
FL- -Si- O — Sr O — Si O— Si — R,
(CH2)3
CH, CH, CH,
NH (CH2)2
NH. (XIV) in which p and q are numbers such that the sum (p + q) can range especially from 1 to
1000, in particular from 50 to 350 and more particularly from 150 to 250, p possibly denoting a number from 0 to 999, especially from 49 to 349 and more particularly from 159 to 239, and q possibly denoting a number from 1 to 1000, especially from 1 to 10 and more particularly from 1 to 5,
R1 and R2, which are different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 and R2 denoting an alkoxy radical
Preferably, the alkoxy radical is a methoxy radical
42 Composition according to the preceding claim, characterized in that the hydroxyl/alkoxy mole ratio is preferably between 1 0 8 and 1 1 1 , preferably between 1 0 9 and 1 1 and is more particularly equal to 1 0 95
43 Composition according to any one of the preceding claims, characterized in that the amino silicone is in the form of an oιl-ιn-water emulsion
44 Composition according to the preceding claim, characterized in that the emulsion comprises one or more surfactants, which are preferably cationic and/or nonionic
45 Composition according to any one of the preceding claims, characterized in that the amino silicone is present in a concentration ranging from 0 001 % to 20% by weight and preferably from 0 01 % to 10% by weight relative to the total weight of the composition
46 Composition according to any one of the preceding claims, characterized in that it comprises at least one additional direct dye other than the compounds of formula I.
47. Composition according to Claim 36, characterized in that the additional direct dye(s) is (are) present in a concentration ranging from 0.001% to 20% by weight relative to the total weight of the composition.
48. Composition according to any one of the preceding claims, characterized in that it also comprises an oxidizing agent.
49. Composition according to any one of the preceding claims, characterized in that it comprises at least one oxidation base chosen from the group formed by para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.
50. Composition according to Claim 49, characterized in that the oxidation base(s) is (are) present in a concentration ranging from 0.001 % to 10% by weight relative to the total weight of the composition.
51. Composition according to either of Claims 49 and 50, characterized in that it comprises at least one coupler chosen from the group formed by meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
52. Composition according to Claim 51 , characterized in that the coupler(s) is (are) present in a concentration ranging from 0.001% to 10% by weight relative to the total weight of the composition.
53. Process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, characterized in that at least one dye composition as defined in any one of Claims 1 to 52 is applied to the fibres for a time that is sufficient to obtain the desired coloration, after which the fibres are rinsed, optionally washed with shampoo, rinsed again and dried.
54. Process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, characterized in that at least one dye composition as defined in any one of Claims 1 to 52 is applied to the fibres for a time that is sufficient to obtain the desired coloration, without final rinsing.
55. Multi-compartment device or multi-compartment dyeing "kit", characterized in that a first compartment contains a composition comprising the cationic direct dye as defined 1 to 47 and a second compartment containing an oxidising agent.
PCT/EP2006/069928 2005-12-22 2006-12-19 Composition for dyeing keratin fibres with a tetraazapentamethine cationic direct dye and an amino silicone Ceased WO2007071684A2 (en)

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FR0554058 2005-12-22
FR0554058A FR2895242B1 (en) 2005-12-22 2005-12-22 DYE COMPOSITION FOR KERATINOUS FIBERS WITH TETRAAZAPENTA-METHINIC CATIONIC DIRECT COLORANT AND AMINE SILICONE
US76175006P 2006-01-25 2006-01-25
US60/761,750 2006-01-25

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