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WO2007071686A1 - Composition for dyeing keratin fibres with a tetraazapentamethine cationic direct dye, an oxidation base and a particular coupler - Google Patents

Composition for dyeing keratin fibres with a tetraazapentamethine cationic direct dye, an oxidation base and a particular coupler Download PDF

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Publication number
WO2007071686A1
WO2007071686A1 PCT/EP2006/069932 EP2006069932W WO2007071686A1 WO 2007071686 A1 WO2007071686 A1 WO 2007071686A1 EP 2006069932 W EP2006069932 W EP 2006069932W WO 2007071686 A1 WO2007071686 A1 WO 2007071686A1
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Prior art keywords
formazano
chloride
pyridinylidene
triazole
methyl
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PCT/EP2006/069932
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French (fr)
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Alain Lagrange
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LOreal SA
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LOreal SA
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Priority claimed from FR0554060A external-priority patent/FR2895244B1/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
    • 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
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • 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
    • A61Q5/10—Preparations for permanently dyeing the hair

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 oxidation base and at least one particular coupler.
  • 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 oxidation base and (iii) at least one nitrogenous heterocyclic coupler:
  • 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 2 i,
  • - Z 1 represents an oxygen or sulfur atom or a radical NR 9
  • - Z 2 represents a nitrogen atom or a radical CR 1 0,
  • - 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 ,
  • 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),
  • R 2 , Re, Rio and R 16 represent, independently of each other, a hydrogen atom; a linear or branched C 1 -C 4 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; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, C 2
  • R 1 , R 4 , R 5 , R 7 , Rg, R 15 , 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;
  • - R 0 , R3, Rs, R11, Ri 2 , Ri3, Ri 4 , Ri 7 , R18, Ri9 and R 20 represent, independently of each other, a hydrogen atom, a linear or branched C 1 -C 1 6 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, Ci-C 2 alkoxy, C 2
  • R 0 , R3, Rs, Rn, Ri 2 , R 1 3, Ri 4 , Ri 7 , R 18 , R 1 9 and R 20 do not comprise a peroxide bond or diazo or nitroso radicals
  • - R 2 with R 10 , R 11 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)(CrC 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— CH 2 -H can become j — 0 ⁇
  • 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 (C-i-C ⁇ Jalkylsulfonate such as methyl sulfonate; an arylsulfonate, which is unsubstituted or substituted with a C 1 -C 4 alkyl 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
  • R 0 represents a hydrogen atom; a linear or branched C 1 -C 6 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, 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, C 1 -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, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl,
  • R 0 preferably represents a hydrogen atom; a linear or branched CrC 3 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, CrC 2 alkoxy, amino, CrC 2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, CrC 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 represents a hydrogen atom; a methyl, ethyl, propyl, butyl, 2-hydroxyethyl, 2-aminoethyl, 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl or 2-methoxyethyl; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from amino, CrC 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.
  • Ro 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 , Rio 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 R 16 preferably represent a hydrogen atom, a methyl, phenyl or 2-hydroxymethyl radical, a carboxyl or a phenyl radical.
  • Ri, R 4 , R5, R7, R9, Ri5, R 21 and R 22 preferably represent a C 1 -C 4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C 1 -C 2 alkoxy, amino, C 1 -C 2 (di)alkylamino, carboxyl and sulfonic radicals.
  • R 1 , R 4 , R 5 , R 7 , Rg, R 15 , R 21 and R 22 preferably represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl or 2- sulfonylethyl radical.
  • R 3 , Rs, Rii, Ri2, Ri3, Ri4, Ri7, Ri8, Ri9 and R 2 o preferably represent, independently of each other, a hydrogen atom; a linear or branched CrC 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
  • R 3 , R 8 , Rn, Ri 2 , Ri 3 , Ri 4 , R 1 7, R 1 8, R 1 9 and R 20 represent a hydrogen atom, a Ci-C 4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl radicals or a CrC 2 alkoxy radical; an amino radical; a CrC 2 (di)alkylamino radical; a carboxyl radical; a C 2 -C 4 (poly)hydroxyalkylamino radical.
  • R 3 , R 8 , Rn, Ri 2 , Ri 3 , R 14 , R 1 7, R 1 8, R 1 9 and R 2 o 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 Wi is a 2-pyridinium 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]-N-methylpyridinium chloride
  • 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:
  • 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: - 2-[5-(N-methyl-2-pyridinylidene)-1-formazano]-1 ,3-dimethylbenzimidazolium 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 4- pyridine radical. Even more preferably, they are the following compounds: - 2-[5-(N-methyl-4-pyridinylidene)-1-formazano]-1 ,3-dimethylbenzimidazolium 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-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 4-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 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 R 25 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 , R 2 6 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 2 3CHO 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' 2 3 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 , Z 16 and R 25 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,
  • 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°C and 80°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, phenylpyruvate 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 4- 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 nitroethane
  • 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 alkenylglycerophosphocholine
  • alkenylglycerophosphoethanolamine hydrolase EC 3.3.2.5
  • alkenylglycerophosphocholine alkylalidase
  • 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 4.1.2.1 1 (hydroxymandelonitrile), ketopantoaldolase EC 4.1.2.12 (2-hydroxy-2-isopropylbutanedioate), dimethylaniline-N-oxide aldolase EC 4.1.2.24 (dimethylaniline-N-oxide), phenylserine al
  • 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
  • the reaction may be performed between pH 3 and pH 1 1 and preferably between pH 5 and pH 9.5.
  • the reaction temperature may be between 10°C and 80°C and preferably between 20°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 , R 0 , R 24 and R 25 for formula F1 and Z 17 , Z 18 , Z 19 , Z 20 , R 0 , R 24 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" 2 3C(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°C and 180°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°C for a period of between 30 minutes and 12 hours.
  • the protic solvent is chosen from H 2 O, ethanol and methanol.
  • the dye composition in accordance with the invention contains, in addition to the cationic direct dye(s), (i) one or more oxidation bases (ii).
  • oxidation bases are preferably 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 1 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 (CrC 4 )alkoxy(CrC 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 (CrC 4 )alkoxy(CrC 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 C 1 -C 4 alkyl radical, a sulfo radical, a carboxy radical, a C 1 -C 4 monohydroxyalkyl radical, a C 1 -C 4 hydroxyalkoxy radical, an acetylamino(CrC 4 )alkoxy radical, a C 1 -C 4 mesylaminoalkoxy radical or a carbamoylamino(C 1 -C 4 )alkoxy radical,
  • a halogen atom such as a chlorine atom, a C 1 -C 4 alkyl radical, a sulfo radical, a carboxy radical, a C 1 -C 4 monohydroxyalkyl radical, a C 1 -C 4 hydroxyalkoxy radical, an acetylamino(CrC 4 )alkoxy radical, a C 1 -C 4 mesylaminoal
  • R 4 represents a hydrogen or halogen atom or a C 1 -C 4 alkyl radical.
  • nitrogenous groups of formula (Vl) above mention may be made in particular of amino, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino, tri(C 1 -C 4 )alkylamino, monohydroxy(C 1 - C 4 )alkylamino, imidazolinium and ammonium radicals.
  • para-phenylenediamines of formula (Vl) above examples include para-phenylenediamine, para-tolylenediamine, 2-chloro-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,
  • para-phenylenediamines of formula (Vl) above 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 (VII) below, and the addition salts thereof with an acid: z. Z n
  • - Z 1 and Z 2 which may be identical or different, represent a hydroxyl or -NH 2 group that may be substituted with a d-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 CrC 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, R 1O , Rn and R 12 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 (VII) contain only one linker arm Y per molecule.
  • nitrogenous groups of formula (VII) above mention may be made in particular of amino, mono(Ci-C 4 )alkylamino, di(Ci-C 4 )alkylamino, tri(Ci-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 C 1 -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, R 14 represents a hydrogen atom or a halogen atom such as fluorine, a C ⁇ C 4 -alkyl,
  • para-aminophenols of formula (VIII) above mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-
  • 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- methoxypyridine, 2-( ⁇ -methoxyethyl)amino-3-amino-6-methoxy pyridine 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, 4- 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.
  • nitrogenous heterocyclic coupler (iii) means any coupler containing in its structure at least one 4- to 8-membered ring, at least one of these ring members including a nitrogen atom.
  • This ring may comprise several nitrogen atoms among its ring members and optionally one or more heteroatoms chosen from sulfur and oxygen.
  • This ring may be isolated or fused to one or more other rings, these additional rings optionally comprising one or more heteroatoms chosen from nitrogen, sulfur and oxygen.
  • the ring(s) forming part of the structure of the nitrogenous heterocycle of the invention may be optionally substituted with one or more identical or different substituents.
  • substituents are preferably chosen from C 1 -C 1 0 alkyl, hydroxyl, amino, mono- or di(Cr C 6 )alkylamino, monohydroxy- or dihydroxy(Ci-C 6 )alkylamino, mono(Ci-C 6 )alkylmonohydroxy- (CrC ⁇ Jalkylamino, C 2 -C 1 0 acyl, monohydroxy- or polyhydroxy(Ci-Cio)alkyl, carboxyl, sulfo and cyano radicals.
  • heterocyclic couplers that may be used in the composition according to the invention, mention may be made especially of pyridine derivatives, benzimidazole derivatives, benzomorpholine derivatives, pyrazoloazole derivatives, pyrroloazole derivatives, imidazoloazole derivatives, pyrazolopyrimidine derivatives, hydroxy- pyrazolopyrimidine derivatives, pyrazoline-3,5-dione derivatives, pyrrolo[3,2-d]oxazole derivatives, pyrazolo[3,4-d]thiazole derivatives, thiazoloazole S-oxide derivatives, thiazoloazole S,S-dioxide derivatives, carbazole derivatives, hydroxyindazole derivatives, benzoxazole derivatives, thiazoloazole derivatives, imidazoloazole derivatives, isoxazolone derivatives, indazolone derivatives, indole derivatives, indoline derivatives and
  • R 14 represents a hydrogen atom, a hydroxyl, C 1 -C 4 alkoxy, C 1 -C 4 monohydroxyalkoxy, C 2 -C 4 polyhydroxyalkoxy, amino, C 1 -C 4 mono- or dialkylamino, C 1 -C 4 mono- or di(hydroxyalkyl)amino radical or a group -OCH 2 CH 2 COCH 2 CH 2 OH,
  • R- I5 and R 17 which may be identical or different, represent a hydrogen atom or a hydroxyl, amino or C 1 -C 4 alkyl radical,
  • R 16 represents a hydrogen atom or a C 1 -C 4 alkyl radical
  • R 18 represents a hydrogen atom or a hydroxyl, C 1 -C 4 alkoxy, C 1 -C 4 monohydroxyalkoxy, C 2 -
  • pyridine derivatives of formula (IX) above that may be used as nitrogenous heterocyclic couplers in the compositions in accordance with the invention, mention may be made more particularly of 2-amino-3-hydroxypyridine, 2,6-dihydroxy-4-methylpyridine, 2,6- dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-bis( ⁇ - hydroxyethyl)oxy-3,5-diaminopyridine, 3-amino-2,6-dimethoxy-5-hydroxypyridine, 2,6- diaminopyridine, 3-oxo-5-(3',5'-diamino-2'-pyridyloxy)pentanol and 3-(3',5'-diamino-2'- pyridyloxy)-2-hydroxypropanol, and the addition salts thereof with an acid.
  • benzimidazole derivatives that may be used as nitrogenous heterocyclic coupler
  • R 5 represents a hydrogen atom or a C 1 -C 4 alkyl radical
  • R 6 represents a hydrogen atom or a C 1 -C 4 alkyl or phenyl radical
  • R 7 represents a hydroxyl, amino or methoxy radical
  • R 8 represents a hydrogen atom or a hydroxyl, methoxy or C 1 -C 4 alkyl radical
  • benzimidazole derivatives that may be mentioned more particularly are 4,7- dihydroxybenzimidazole, 4,7-dihydroxy-1 -methylbenzimidazole, 4,7-dihydroxy-2-methyl- benzimidazole, 4,7-dihydroxy-1 -ethylbenzimidazole, 4,7-dihydroxy-1 -propylbenzimidazole, 4,7-dihydroxy-1-butylbenzimidazole, 4,7-dihydroxy-2-ethylbenzimidazole, 4,7-dihydroxy-2- butylbenzimidazole, 4,7-dihydroxy-1 ,2-dimethylbenzimidazole hydrobromide, 4,7-dimethoxy- benzimidazole, 4,7-dimethoxy-1 -methylbenzimidazole, 4,7-dimethoxy-1 -ethylbenzimidazole, 4,7-dimethoxy-2-methyl-benzimidazole, 4,7-dimethoxy-2-ethylbenz
  • benzomorpholine derivatives that may be used as nitrogenous heterocyclic couplers in the dye composition in accordance with the invention, mention may be made more particularly of the compounds of formula (Xl) below, and the addition salts thereof with an acid:
  • R 9 and Ri 0 which may be identical or different, represent a hydrogen atom or a CrC 4 alkyl radical, Z represents a hydroxyl or amino radical.
  • benzomorpholine derivatives that may be mentioned more particularly are 6- hydroxy-1 ,4-benzomorpholine, N-methyl-6-hydroxy-1 ,4-benzomorpholine and 6-amino-1 ,4- benzomorpholine, and the addition salts thereof with an acid.
  • Pyrazoloazoles that may be mentioned include pyrazolo[1 ,5-b]-1 ,2,4-triazoles, pyrazolo[3,2- c]-1 ,2,4-triazoles, pyrazolotetrazoles, pyrazolo[1 ,5-a]imidazoles, pyrazolo[1 ,5-e]pyrazoles and pyrazolo[1 ,5-e]-1 ,2,3-triazoles.
  • the pyrazolo[1 ,5-b]-1 ,2,4-triazoles are chosen from 2-methylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2- phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2- ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6- methyl-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-
  • the pyrazolo[3,2-c]-1 ,2,4-triazoles are chosen from 3-methylpyrazolo[3,2-c]-1 ,2,4- triazole, 3-methylsulfinyl-6-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-ethylpyrazolo[3,2-c]-1 ,2,4- triazole, 3-isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 3- (2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 3-(2'-hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 3,6-dimethylpyrazolo[3,2-c]
  • the pyrazolotetrazoles are chosen from pyrazolo[5,1-e]tetrazole, 6- methylpyrazolo[5, 1 -e]tetrazole, 6-phenylpyrazolo[5, 1 -e]tetrazole, 6-carboxypyrazolo[5, 1 - e]tetrazole and 7-chloro-6-methylpyrazolo[5,1-e]tetrazole, and the addition salts thereof with an acid.
  • the pyrazolo[1 ,5-a]imidazoles are chosen from pyrazolo[1 ,5-a]imidazole, 2- methylpyrazolo[1 ,5-a]imidazole, 2-phenylpyrazolo[1 ,5-a]imidazole, pyrazolo[1 ,5- a]benzimidazole, 6-methylpyrazolo[1 ,5-a]imidazole, 2,6-dimethylpyrazolo[1 ,5-a]imidazole, 6- methyl-2-phenylpyrazolo[1 ,5-a]imidazole, 6-methylpyrazolo[1 ,5-a]benzimidazole, 6- phenylpyrazolo[1 ,5-a]imidazole, 6-phenyl-2-methylpyrazolo[1 ,5-a]imidazole, 2,6- diphenylpyrazolo[1 ,5-a]imid
  • the pyrazolo[5,1-e]pyrazoles are chosen from 8-amino-4-methylpyrazolo[5,1- e]pyrazole and 8-amino-5-chloro-4-methylpyrazolo[5,1-e]pyrazole, and the addition salts thereof with an acid.
  • the pyrazolo[5,1-e]-1 ,2,3-triazoles are chosen from 5-methylpyrazolo[5,1-e]-1 ,2,3- triazole, 5-methyl-6-chloropyrazolo[5,1-e]-1 ,2,3-triazole and 5-phenylpyrazolo[5,1-e]-1 ,2,3- triazole, and the addition salts thereof with an acid.
  • These pyrazoloazoles are described in patent application WO 97/35551 , and the pages in the said prior art patent application devoted to pyrazoloazoles and to their synthesis is incorporated into the present patent application by reference.
  • pyrroloazoles that may be used in the compositions according to the present patent application, mention may be made of pyrazolo[1 ,2-b]-1 ,2,4-triazoles, pyrrolo[2,1-c]-1 ,2,4- triazoles, pyrrolo[1 ,2-c]imidazoles, pyrrolo[1 ,2-e]tetrazoles, pyrrolo[1 ,2-a]pyrroles, pyrrolo[1 ,2-a]imidazoles and pyrrolo[1 ,2-c]-1 ,2,3-triazoles.
  • the pyrrolo[1 ,2-b]-1 ,2,4-triazoles are chosen from 3,4-dicyano-8- methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3,4-dicyano-8-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3,4- dicyano-8-tert-butylpyrrolo[1 ,2-b]-1 ,2,4-triazole and 5-chloro-3,4-dicyano-8-methylpyrrolo[1 ,2- b]-1 ,2,4-triazole, and also 5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 5- cyano-4-carboxy-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,5-dicyano-8-methylpyrrolo[1 ,2-b]- 1 ,2,4
  • the pyrrolo[2,1-c]-1 ,2,4-triazoles are chosen from 5,6-dicyano-3- methylpyrrolo[2,1-c]-1 ,2,4-triazole and /-chloro- ⁇ . ⁇ -dicyano-S-methylpyrroloP.I-cl-i ,2,4- triazole, and also 6,7-dicyano-3-methylpyrrolo[2,1-c]-1 ,2,4-triazole, 5-chloro-6,7-dicyano-3- methylpyrrolo[2,1-c]-1 ,2,4-triazole, 6,7-bis(ethoxycarbonyl)-3-methylpyrrolo[2,1-c]-1 ,2,4- triazole, 7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]-1 ,2,4-triazole and 7-cyano-3-methyl-6-tert- butylpyrrolo[2,1-c]-1 ,2,2,4-
  • the pyrrolo[1 ,2-c]imidazoles are chosen from 6,8-dicyano-5- ethoxycarbonylpyrrolo[1 ,2-c]imidazole and 4-chloro-6,8-dicyano-5-ethoxycarbonylpyrrolo[1 ,2- c]imidazole, and the addition salts thereof with an acid.
  • the pyrrolo[1 ,2-e]tetrazoles are chosen from 6,7-dicyanopyrrolo[1 ,2-e]tetrazole, 6- cyano-7-ethoxycarbonylpyrrolo[1 ,2-e]tetrazole and 5-chloro-6,7-dicyanopyrrolo[1 ,2- e]tetrazole, and the addition salts thereof with an acid.
  • the pyrrolo[1 ,2-a]imidazoles are chosen from 2,3,7-tricyano-6-methylpyrrolo[1 ,2- a]imidazole, 2,3,7-tricyano-6-trifluoromethylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6-tert- butylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6-phenylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6- ethoxycarbonylpyrrolo[1 ,2-a] imidazole, 5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1 ,2-a]imid- azole, 5-chloro-2,3,7-tricyano-6-phenylpyrrolo[1 ,2-a]imidazole, 7-cyano-6- ethoxycarbonylpyrrolo [1 ,
  • the pyrrolo[1 ,2-c]-1 ,2,3-triazoles are chosen from 5,6,8-tricyanopyrrolo[1 ,2-c]- 1 ,2,3-triazole, 5,8-tricyano-6-ethoxycarbonylpyrrolo[1 ,2-c]-1 ,2,3-triazole and 4-chloro-5,8- dicyano-6-ethoxycarbonylpyrrolo[1 ,2-c]-1 ,2,3-triazole, and the addition salts thereof with an acid.
  • Imidazoloazole derivatives that may be mentioned most particularly are:
  • hydroxypyrazolopyrimidine derivatives that are used in the compositions according to the present patent application, mention may be made of hydroxypyrazolo[1 ,5-a]pyrimidines and more particularly 2-hydroxy-5-methyl-7-ethylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-5,6,7- trimethylpyrazolo[1 ,5-a] pyrimidine, 2-hydroxy-5,7-dimethyl-6-ethylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-7-methylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-5-methyl-7-carboxypyrazolo[1 ,5- a]pyrimidine and 2,7-dihydroxy-5,6-dimethylpyrazolo[1 ,5-a]pyrimidine.
  • These hydroxypyrazolopyrimidines are described in patent application DE 4029324, and the passage in the said prior art patent application devoted to hydroxypyrazolopyrimidine
  • Carbazole derivatives that may be mentioned include 1 ,3,6,8-tetraaminocarbazole, 1 ,3,6,8- tetraamino-9-n-propylcarbazole, 1 ,3,6,8-tetraamino-9- ⁇ -hydroxyethylcarbazole and 1 ,3,6,8- tetraamino-9-(2'-N,N-dimethylaminoethyl)carbazole. These compounds are described in patent application DE 2715680, and the passage in the said prior art patent application devoted to carbazoles and to their synthesis is incorporated into the present patent application by reference.
  • a carbazole that may also be mentioned is 3-aminocarbazole, described in patent application DE 277 496.
  • Hydroxyindazole derivatives that may be mentioned include the following monohydroxyindazoles: 4-hydroxyindazole, 5-hydroxyindazole, 6-hydroxyindazole, 7- hydroxyindazole, 7-hydroxy-1-methylindazole, 4-hydroxy-6-methylindazole, 7-hydroxy-6- methylindazole, 7-hydroxy-4,6-dimethylindazole, 6-hydroxy-7-bromoindazole, 6-hydroxy-7- chloroindazole and 6-hydroxy-5,7-dichloroindazole.
  • These hydroxyindazoles are described in patent application DE 26 23 564, and the passage in the said prior art patent application devoted to hydroxyindazoles and to their synthesis is incorporated into the present patent application by reference.
  • Benzoxazole derivatives that may be mentioned include the following diaminobenzoxazoles: 5,7-diaminobenzoxazole, 5,7-diamino-2-methylbenzoxazole, 5,7-diamino-2- ethylbenzoxazole, 5,7-diamino-2-butylbenzoxazole, 5-dimethylamino-7-aminobenzoxazole, 5-amino-7-diethylaminobenzoxazole and 4,6-diaminobenzoxazole.
  • imidazoloazole derivatives that are used in the compositions according to the present invention, mention may be made of imidazolo[3,2-a]imidazoles, imidazolo[1 ,2-b]-1 ,2,4- triazoles and imidazolo[2,1-c]-1 ,2,4-triazoles.
  • the imidazolo[3,2-a]imidazoles are chosen from 7,8-dicyanoimidazolo[3,2- a]imidazole, 7,8-dicyano-4-methylimidazolo[3,2-a] imidazole, 7,8-dicyano-4- ethylimidazolo[3,2-a]imidazole, 7,8-dicyano-4-isopropylimidazolo[3,2-a]imidazole, 7,8- dicyano-4-phenylimidazolo[3,2-a]imidazole, 5-chloro-7,8-dicyano-4-methylimidazolo[3,2- a]imidazole and 7,8-dicyano-4-trifluoromethylimidazolo[3,2-a]imidazole, and the addition salts thereof with an acid.
  • the imidazolo[1 ,2-b]-1 ,2,4-triazoles are chosen from imidazolo[1 ,2-b]-1 ,2,4- triazole, 6-methylimidazolo[1 ,2-b]-1 ,2,4-triazole, 6-isopropylimidazolo-[1 ,2-b]-1 ,2,4-triazole,
  • the imidazolo[2,1-c]-1 ,2,4-triazoles are chosen from imidazolo[2,1-c]-1 ,2,4- triazole, 5-methylimidazolo[2,1-c]-1 ,2,4-triazole, 5,8-dimethylimidazolo[2,1-c]-1 ,2,4-triazole, 5-methyl-8-phenylimidazolo[2,1-c]-1 ,2,4-triazole, 8-phenylimidazolo[2,1-c]-1 ,2,4-triazole and 6-chloro-5,8-dimethylimidazolo[2,1-c]-1 ,2,4-triazole, and the addition salts thereof with an acid.
  • imidazoloazoles are described in patent application WO 97/35552, and the passage in the said prior art patent application devoted to imidazoloazoles and to their synthesis is incorporated into the present patent application by reference.
  • isoxazolone derivatives that are used in the compositions according to the present patent application, mention may be made of 4-carboxy- ⁇ : ⁇ -benzisoxazolone, 1-acetyl-4-carboxy- ⁇ : ⁇ -benzisoxazolone, 6-carboxy- ⁇ : ⁇ -benzisoxazolone, 1-acetyl-6-carboxy- ⁇ : ⁇ - benzisoxazolone, ⁇ : ⁇ -benzisoxazolone, 1-acetyl- ⁇ : ⁇ -benzisoxazolone, 4-methyl- ⁇ : ⁇ - benzisoxazolone, 1-acetyl-4-( ⁇ -hydroxyethylamino)carbonyl- ⁇ : ⁇ -benzisoxazolone, 3-phenyl- 5-isoxazolone, 2-acetyl-3-phenyl-5-isoxazolone, 3,4-diphenyl-5-isoxazolone, 3-methyl-5- isoxazolone and 3,4-te
  • indazolone derivatives that are used in the compositions according to the present patent application, mention may be made of indazolone, 5-chloroindazolone, 6-chloroindazolone, 1- ethylindazolone, 5-dimethylaminoindazolone, 1-methylindazolone, 1-isopropylindazolone, 1- butylindazolone, 3-chloroindazolone, 4-chloroindazolone, 5-methylindazolone, 6- methylindazolone, 5-ethylindazolone, 6-propylindazolone, 5-butylindazolone, 1 ,5- dimethylindazolone, 1 ,6-dimethylindazolone, 1-methyl-5-chloroindazolone, 1-methyl-6- chloroindazolone, 1-ethyl-5-chloroindazolone, 1-ethyl-6-bromoindazolone, 5- aminoindazolone, 6-di
  • Indole derivatives that may be mentioned include the compounds of formulae (XII) and (XIII) below, or the addition salts thereof with an acid:
  • R 13 represents a hydrogen atom, a CrC 4 alkyl radical or a CrC 4 hydroxyalkyl radical
  • Ri 4 and Ri 5 which may be identical or different, represent a hydrogen atom or a d-C 4 alkyl, carboxyl or (Ci-C 4 )alkoxycarbonyl radical;
  • X represents a hydrogen or halogen atom or a C r C 4 alkyl, Ci-Ci 8 alkoxy or acetylamino radical
  • Ri 6 and Ri 7 which may be identical or different, represent a hydrogen atom or a Ci-C 4 alkyl radical; Ri8 represents a hydrogen atom or a CrC 4 alkyl or hydroxyl radical;
  • Y represents a hydroxyl radical or NHRi 9 in which Ri 9 represents a hydrogen atom or a d-
  • Indole derivatives that may be mentioned most particularly include 6-hydroxyindole, 4- hydroxy-1 N- ⁇ -hydroxyethylindole and 5,6-dihydroxyindole, and the addition salts thereof with an acid.
  • lndoline derivatives that may be mentioned most particularly include 6-hydroxyindoline, 6- aminoindoline and 5,6-dihydroxyindoline, and the addition salts thereof with an acid.
  • R ig denotes a hydroxyl or CrC 4 alkoxy radical and R 2 0 denotes a hydrogen atom or an amino radical.
  • the nitrogenous heterocycles comprise, among the ring members constituting the rings, only nitrogen atoms as heteroatoms in addition to the carbon atoms.
  • the nitrogenous heterocyclic couplers of the invention are chosen from pyridines, indoles and indolines.
  • the nitrogenous heterocyclic coupler(s) each represent(s) from 0.0001 % to 12% by weight approximately relative to the total weight of the composition according to the invention, and preferably from 0.005% to 6% by weight relative to the total weight of the composition.
  • compositions of the invention may contain one or more additional couplers other than the nitrogenous heterocyclic couplers of the invention.
  • the additional 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 non-nitrogenous heterocyclic couplers, for instance sesamol and derivatives thereof, and the addition salts thereof with an acid.
  • additional 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 and ⁇ -naphthol, and the addition salts thereof with an acid.
  • the additional 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 addition salts with an acid of the oxidation bases and couplers are especially chosen from the hydrochlorides, hydrobromides, sulfates, tartrates, lactates and acetates.
  • 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 CrC 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 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.
  • 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.
  • 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.
  • 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:
  • the dye compositions in accordance with the invention may contain one or more other 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 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) of formula (I) with a composition containing at least one oxidation base and at least one nitrogenous heterocyclic coupler as defined above.
  • 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.
  • 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 optionally a composition (C1 ) in a suitable dyeing medium, and then in mixing together at the time of use compositions (A1 ) and (B1 ) and optionally (C1 ), followed by applying this mixture to keratin fibres, composition (A1 ) and/or composition (C1 ) containing at least one oxidation base and at least one nitrogenous heterocyclic coupler 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 ) as defined above, a second compartment contains composition (B1 ), and optionally a third compartment contains composition (C1 ) 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):
  • this composition is mixed weight for weight with 20-volumes aqueous hydrogen peroxide solution at pH 3.
  • the mixture is 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 (20°C).
  • the locks are rinsed, shampooed and then rinsed and dried. They are dyed in a sparingly selective chromatic violet-blond shade.

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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 oxidation base and at least one particular coupler. 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, AN OXIDATION BASE AND A PARTICULAR COUPLER
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 oxidation base and at least one particular coupler.
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 tetraazapentamethine cationic direct dye known in the prior art, at least one oxidation base and at least one particular heterocyclic coupler.
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 oxidation base and (iii) at least one nitrogenous heterocyclic coupler:
Figure imgf000003_0001
in which
W1 represents a cationic heteroaromatic radical of formula (II) or (III):
Figure imgf000003_0002
(H) (TO)
W2 represents a heteroaromatic radical of formula (IV) or (V):
Figure imgf000004_0001
(W) (V) in which:
- Z0 represents a radical CR2, a nitrogen atom or a radical NR2i,
- 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 Z11 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, Re, Rio 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 or two 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, R15, 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, R11, Ri2, Ri3, Ri4, Ri7, R18, 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, Ci-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, d-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, CrC2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, CrC2 (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, Ri2, R13, Ri4, Ri7, R18, R19 and R20 do not comprise a peroxide bond or diazo or nitroso radicals, - R2 with R10, R11 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)(CrC2)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: j— CH2-H can become j — 0^
Figure imgf000006_0001
I >*v^ y^ can become I -^^*-;cr 1N.
Figure imgf000006_0002
j — CHJ- CHJ can become | — 0-CH1
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 (C-i-CβJalkylsulfonate such as methyl sulfonate; an arylsulfonate, which is unsubstituted or substituted with a C1-C4 alkyl radical, for instance a 4- tolylsulfonate.
Preferably, R0 represents a hydrogen atom; a linear or branched C1-C6 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, 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 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 CrC3 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, CrC2 alkoxy, amino, CrC2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, CrC2 (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-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl or 2-methoxyethyl; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from amino, CrC2 (di)alkylamino and C2-C4 (poly)hydroxyalkylamino radicals, or an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl and pyridyl radicals.
Ro 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, Rio 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 R16 preferably represent a hydrogen atom, a methyl, phenyl or 2-hydroxymethyl radical, a carboxyl or a phenyl radical.
Ri, R4, R5, R7, R9, Ri5, 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.
According to one particularly preferred embodiment, R1, R4, R5, R7, Rg, R15, R21 and R22 preferably represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl or 2- sulfonylethyl radical.
R3, Rs, Rii, Ri2, Ri3, Ri4, Ri7, Ri8, Ri9 and R2o preferably represent, independently of each other, a hydrogen atom; a linear or branched CrC4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, C1-C2 alkoxy, C2-C4
(poly)hydroxyalkoxy, amino, CrC2 (di)alkylamino, carboxyl and sulfonic radicals; a phenyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl,
CrC2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, CrC2 (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, Ri2, Ri3, Ri4, R17, R18, R19 and R20 represent a hydrogen atom, a Ci-C4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl radicals or a CrC2 alkoxy radical; an amino radical; a CrC2 (di)alkylamino radical; a carboxyl radical; a C2-C4 (poly)hydroxyalkylamino radical.
According to one particularly preferred embodiment, R3, R8, Rn, Ri2, Ri3, R14, R17, R18, R19 and R2o 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 Wi 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 -forrnazano]-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 -forrnazano]-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-pyπdinylidene)-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-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-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
- 5-[5-(1 ,2-dicarboxyethyl-5-pyrazolidene)-3-(4'-N,N-dimethylaminophenyl)-1-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- 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-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 4- 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-pyπdinylidene)-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-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
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)-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- 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-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-dimethylamino-phenyl)-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 imgf000021_0001
BY*
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, 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 having 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, 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 6°C and 80°C.
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, phenylpyruvate 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 4- 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 1.13.1 1.17 (indole), taurine dioxygenase EC 1.14.1 1.17 (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 4.1.2.1 1 (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-hydroxyphenyl)- 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-Cβ 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 1 1 and preferably between pH 5 and pH 9.5.
The reaction temperature may be between 10°C and 80°C and preferably between 20°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.
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 imgf000026_0001
Formula Fl Formula F2 with Z14, Z15, Z16, R0, R24 and R25 for formula F1 and Z17, Z18, Z19, Z20, R0, 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 66°C and 180°C. 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 150°C for a period of between 30 minutes and 12 hours.
Preferably, the protic solvent is chosen from H2O, ethanol and methanol.
The dye composition in accordance with the invention contains, in addition to the cationic direct dye(s), (i) one or more oxidation bases (ii). These oxidation bases are preferably 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 (Vl) below, and the addition salts thereof with an acid:
Figure imgf000027_0001
NH, in which:
R1 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a (CrC4)alkoxy(CrC4)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 (CrC4)alkoxy(CrC4)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 C1-C4 alkyl radical, a sulfo radical, a carboxy radical, a C1-C4 monohydroxyalkyl radical, a C1-C4 hydroxyalkoxy radical, an acetylamino(CrC4)alkoxy radical, a C1-C4 mesylaminoalkoxy radical or a carbamoylamino(C1-C4)alkoxy radical,
R4 represents a hydrogen or halogen atom or a C1-C4 alkyl radical.
Among the nitrogenous groups of formula (Vl) above, mention may be made in particular of amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino, tri(C1-C4)alkylamino, monohydroxy(C1- C4)alkylamino, imidazolinium and ammonium radicals.
Examples of para-phenylenediamines of formula (Vl) above that may especially be mentioned include para-phenylenediamine, para-tolylenediamine, 2-chloro-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,
N,N-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)- paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl- para-phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-para-phenylene diamine, N-(β,γ- dihydroxypropyl)-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 (Vl) 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 (VII) below, and the addition salts thereof with an acid: z. Zn
R. - , , V — _ ^j- R1,
NfV*v NR.,R j
in which - Z1 and Z2, which may be identical or different, represent a hydroxyl or -NH2 group that may be substituted with a d-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 CrC6 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, R1O, Rn and R12, 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 (VII) contain only one linker arm Y per molecule. Among the nitrogenous groups of formula (VII) above, mention may be made in particular of amino, mono(Ci-C4)alkylamino, di(Ci-C4)alkylamino, tri(Ci-C4)alkylamino, monohydroxy(Ci- C4)alkylamino, imidazolinium and ammonium radicals.
Among the double bases of formula (VII) 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- hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)- tetramethylenediamine, 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 (VII), 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 (VIII) below, and the addition salts thereof with an acid:
Figure imgf000029_0001
NH? in which:
R13 represents a hydrogen atom, a halogen atom such as fluorine, a C1-C4 alkyl, C1-C4 monohydroxyalkyl, (C1-C4)alkoxy(C1-C4)alkyl, C1-C4 aminoalkyl or hydroxy(C1-C4)alkylamino(C1-C4)alkyl radical, R14 represents a hydrogen atom or a halogen atom such as fluorine, a CτC4-alkyl,
C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl, C1-C4 cyanoalkyl or (Ci-C4)alkoxy(Ci-C4)alkyl radical.
Among the para-aminophenols of formula (VIII) 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- methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxy pyridine 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- hydroxyethyl)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, 4- 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.
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.
For the purposes of the present invention, the term "nitrogenous heterocyclic coupler (iii)" means any coupler containing in its structure at least one 4- to 8-membered ring, at least one of these ring members including a nitrogen atom.
This ring may comprise several nitrogen atoms among its ring members and optionally one or more heteroatoms chosen from sulfur and oxygen.
This ring may be isolated or fused to one or more other rings, these additional rings optionally comprising one or more heteroatoms chosen from nitrogen, sulfur and oxygen.
The ring(s) forming part of the structure of the nitrogenous heterocycle of the invention may be optionally substituted with one or more identical or different substituents. These substituents are preferably chosen from C1-C10 alkyl, hydroxyl, amino, mono- or di(Cr C6)alkylamino, monohydroxy- or dihydroxy(Ci-C6)alkylamino, mono(Ci-C6)alkylmonohydroxy- (CrCβJalkylamino, C2-C10 acyl, monohydroxy- or polyhydroxy(Ci-Cio)alkyl, carboxyl, sulfo and cyano radicals.
Among the heterocyclic couplers that may be used in the composition according to the invention, mention may be made especially of pyridine derivatives, benzimidazole derivatives, benzomorpholine derivatives, pyrazoloazole derivatives, pyrroloazole derivatives, imidazoloazole derivatives, pyrazolopyrimidine derivatives, hydroxy- pyrazolopyrimidine derivatives, pyrazoline-3,5-dione derivatives, pyrrolo[3,2-d]oxazole derivatives, pyrazolo[3,4-d]thiazole derivatives, thiazoloazole S-oxide derivatives, thiazoloazole S,S-dioxide derivatives, carbazole derivatives, hydroxyindazole derivatives, benzoxazole derivatives, thiazoloazole derivatives, imidazoloazole derivatives, isoxazolone derivatives, indazolone derivatives, indole derivatives, indoline derivatives and quinoline derivatives, and the addition salts thereof with an acid, alone or as mixtures.
Among the pyridine derivatives that may be used as nitrogenous heterocyclic couplers in the context of the invention, mention may be made especially of the compounds of formula (IX) below, and the addition salts thereof with an acid:
Figure imgf000032_0001
in which:
R14 represents a hydrogen atom, a hydroxyl, C1-C4 alkoxy, C1-C4 monohydroxyalkoxy, C2-C4 polyhydroxyalkoxy, amino, C1-C4 mono- or dialkylamino, C1-C4 mono- or di(hydroxyalkyl)amino radical or a group -OCH2CH2COCH2CH2OH,
R-I5 and R17, which may be identical or different, represent a hydrogen atom or a hydroxyl, amino or C1-C4 alkyl radical,
R16 represents a hydrogen atom or a C1-C4 alkyl radical,
R18 represents a hydrogen atom or a hydroxyl, C1-C4 alkoxy, C1-C4 monohydroxyalkoxy, C2-
C4 polyhydroxyalkoxy or amino radical; at least two of the substituents R14 to R18 being other than hydrogen and two para substituents not possibly denoting an amino or substituted amino group.
Among the pyridine derivatives of formula (IX) above that may be used as nitrogenous heterocyclic couplers in the compositions in accordance with the invention, mention may be made more particularly of 2-amino-3-hydroxypyridine, 2,6-dihydroxy-4-methylpyridine, 2,6- dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-bis(β- hydroxyethyl)oxy-3,5-diaminopyridine, 3-amino-2,6-dimethoxy-5-hydroxypyridine, 2,6- diaminopyridine, 3-oxo-5-(3',5'-diamino-2'-pyridyloxy)pentanol and 3-(3',5'-diamino-2'- pyridyloxy)-2-hydroxypropanol, and the addition salts thereof with an acid. Among the benzimidazole derivatives that may be used as nitrogenous heterocyclic couplers in the dye composition in accordance with the invention, mention may be made more particularly of the compounds of formula (X) below, and the addition salts thereof with an acid:
Figure imgf000033_0001
in which:
R5 represents a hydrogen atom or a C1-C4 alkyl radical, R6 represents a hydrogen atom or a C1-C4 alkyl or phenyl radical, R7 represents a hydroxyl, amino or methoxy radical, R8 represents a hydrogen atom or a hydroxyl, methoxy or C1-C4 alkyl radical; with the proviso that:
- when R7 denotes an amino radical, then it occupies position 4,
- when R7 occupies position 4, then R8 occupies position 7,
- when R7 occupies position 5, then R8 occupies position 6.
Among the benzimidazole derivatives that may be mentioned more particularly are 4,7- dihydroxybenzimidazole, 4,7-dihydroxy-1 -methylbenzimidazole, 4,7-dihydroxy-2-methyl- benzimidazole, 4,7-dihydroxy-1 -ethylbenzimidazole, 4,7-dihydroxy-1 -propylbenzimidazole, 4,7-dihydroxy-1-butylbenzimidazole, 4,7-dihydroxy-2-ethylbenzimidazole, 4,7-dihydroxy-2- butylbenzimidazole, 4,7-dihydroxy-1 ,2-dimethylbenzimidazole hydrobromide, 4,7-dimethoxy- benzimidazole, 4,7-dimethoxy-1 -methylbenzimidazole, 4,7-dimethoxy-1 -ethylbenzimidazole, 4,7-dimethoxy-2-methyl-benzimidazole, 4,7-dimethoxy-2-ethylbenzimidazole, 5,6-dihydroxy- benzimidazole, 5, 6-dihydroxy-1 -methylbenzimidazole, 5, 6-dihydroxy-1 -ethylbenzimidazole, 5,6-dihydroxy-1-butyl-benzimidazole, 5,6-dihydroxy-2-methylbenzimidazole, 5,6-dihydroxy-2- butyl-benzimidazole, 5,6-dihydroxy-2-phenylbenzimidazole hydrobromide, 5,6-dimethoxy- benzimidazole, 5, 6-dimethoxy-1 -methylbenzimidazole, 5,6-dimethoxy-1-ethyl benzimidazole, 5, 6-dimethoxy-1 -propylbenzimidazole, 5,6-dimethoxy-2-methyl benzimidazole, 5,6- dimethoxy-2-butylbenzimidazole, 5,6-dimethoxy-2-phenylbenzimidazole, 5,6-dimethoxy-1 ,2- dimethyl-benzimidazole, 4-hydroxy-7-methoxybenzimidazole, 5-hydroxy-6-methoxy- benzimidazole, 4-hydroxy-7-methoxy-1 -methylbenzimidazole and 5-hydroxy-6-methoxy-1 ,2- dimethyl-benzimidazole. These benzimidazoles are described in patent application DE2812678, and the passage in the said prior art patent application devoted to benzimidazoles and to their synthesis is incorporated into the present patent application by reference.
As benzimidazoles that are used, mention may also be made of the ω- cyanoacetylbenzimidazoles described in general in patent application DE 24 46 632, and in particular 5-amino-1-methyl-2-(ω-cyanoacetyl)benzimidazole. Reference may also be made to the passage in patent application DE 24 46 632 devoted to benzimidazoles and to their synthesis.
Among the benzomorpholine derivatives that may be used as nitrogenous heterocyclic couplers in the dye composition in accordance with the invention, mention may be made more particularly of the compounds of formula (Xl) below, and the addition salts thereof with an acid:
Figure imgf000034_0001
in which: R9 and Ri0, which may be identical or different, represent a hydrogen atom or a CrC4 alkyl radical, Z represents a hydroxyl or amino radical.
Among the benzomorpholine derivatives that may be mentioned more particularly are 6- hydroxy-1 ,4-benzomorpholine, N-methyl-6-hydroxy-1 ,4-benzomorpholine and 6-amino-1 ,4- benzomorpholine, and the addition salts thereof with an acid.
Pyrazoloazoles that may be mentioned include pyrazolo[1 ,5-b]-1 ,2,4-triazoles, pyrazolo[3,2- c]-1 ,2,4-triazoles, pyrazolotetrazoles, pyrazolo[1 ,5-a]imidazoles, pyrazolo[1 ,5-e]pyrazoles and pyrazolo[1 ,5-e]-1 ,2,3-triazoles.
Preferably, the pyrazolo[1 ,5-b]-1 ,2,4-triazoles are chosen from 2-methylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2- phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2- ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6- methyl-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-methylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-carboxy-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-isopropylpyrazolo[1 ,5- b]-1 ,2,4-triazole, 6-carboxy-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2- methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl- 2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6- amino-2-methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-amino-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-amino-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-amino-2-phenylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-ethylthio-2-methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethylthio-2-ethylpyrazolo[1 ,5-b]- 1 ,2,4-triazole, 6-ethylthio-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethylthio-2- phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethoxy-2-methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6- ethoxy-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethoxy-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-ethoxy-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2-(2'- aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-(2'-aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-phenyl-2-(2'-aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethylthio-2-(2'-amino- ethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-(2'-aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-(2'- hydroxyethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2-(2'-hydroxyethyl)pyrazolo[1 ,5-b]-
1 ,2,4-triazole, 6-ethylthio-2-(2'-hydroxyethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-(2'- hydroxyethyl)pyrazolo [1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2-(2'-hydroxyethyl)pyrazolo[1 ,5-b]- 1 ,2,4-triazole, 7-chloro-2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole and 7-bromo-2,6- dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, and the addition salts thereof with an acid.
Preferably, the pyrazolo[3,2-c]-1 ,2,4-triazoles are chosen from 3-methylpyrazolo[3,2-c]-1 ,2,4- triazole, 3-methylsulfinyl-6-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-ethylpyrazolo[3,2-c]-1 ,2,4- triazole, 3-isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 3- (2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 3-(2'-hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 3,6-dimethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6- methyl-3-isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-phenylpyrazolo[3,2-c]-1 ,2,4- triazole, 6-methyl-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-(2'- hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-methylthiopyrazolo[3,2-c]-1 ,2,4- triazole, 6-phenyl-3-methylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3-ethylpyrazolo[3,2-c]- 1 ,2,4-triazole, 6-isopropyl-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3- isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 6- phenyl-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3-(2'-hydroxyethyl)pyrazolo-
[3,2-c]-1 ,2,4-triazole, 6-phenyl-3-methylthiopyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3- methylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6- ethylthio-3-isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3-phenylpyrazolo[3,2-c]-1 ,2,4- triazole, 6-ethylthio-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3-(2'- hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-trifluoromethyl-3-methylthiopyrazolo[3,2-c]- 1 ,2,4-triazole, 6-trifluoromethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3-methylpyrazolo[3,2- c]-1 ,2,4-triazole, 6-carboxy-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3- isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 6- carboxy-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3-(2'- hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 7-chloro-3,6-dimethylpyrazolo[3,2-c]-1 ,2,4- triazole and 7-methoxycarbonyl-3,6-dimethylpyrazolo[3,2-c]-1 ,2,4-triazole, and the addition salts thereof with an acid.
Preferably, the pyrazolotetrazoles are chosen from pyrazolo[5,1-e]tetrazole, 6- methylpyrazolo[5, 1 -e]tetrazole, 6-phenylpyrazolo[5, 1 -e]tetrazole, 6-carboxypyrazolo[5, 1 - e]tetrazole and 7-chloro-6-methylpyrazolo[5,1-e]tetrazole, and the addition salts thereof with an acid.
Preferably, the pyrazolo[1 ,5-a]imidazoles are chosen from pyrazolo[1 ,5-a]imidazole, 2- methylpyrazolo[1 ,5-a]imidazole, 2-phenylpyrazolo[1 ,5-a]imidazole, pyrazolo[1 ,5- a]benzimidazole, 6-methylpyrazolo[1 ,5-a]imidazole, 2,6-dimethylpyrazolo[1 ,5-a]imidazole, 6- methyl-2-phenylpyrazolo[1 ,5-a]imidazole, 6-methylpyrazolo[1 ,5-a]benzimidazole, 6- phenylpyrazolo[1 ,5-a]imidazole, 6-phenyl-2-methylpyrazolo[1 ,5-a]imidazole, 2,6- diphenylpyrazolo[1 ,5-a]imidazole, 6-phenylpyrazolo[1 ,5-a]benzimidazole, 6- carboxypyrazolo[1 ,5-a]imidazole, 6-carboxy-2-methylpyrazolo[1 ,5-a]imidazole, 6-carboxy-2- phenylpyrazolo[1 ,5-a]imidazole, 6-carboxypyrazolo[1 ,5-a]benzimidazole, 6- ethoxypyrazolo[1 ,5-a]imidazole, 6-ethoxy-2-methylpyrazolo[1 ,5-a]imidazole, 6-ethoxy-2- phenylpyrazolo[1 ,5-a]imidazole, 6-trifluoromethylpyrazolo[1 ,5-a]benzimidazole, 6- aminopyrazolo[1 ,5-a]imidazole, 6-amino-2-methylpyrazolo[1 ,5-a]imidazole, 6-amino-2- phenylpyrazolo[1 ,5-a]imidazole, 6-aminopyrazolo[1 ,5-a]benzimidazole, 6-ethylthiopyrazolo- [1 ,5-a]imidazole, 6-ethylthio-2-methylpyrazolo-[1 ,5a]imidazole, 6-ethylthio-2-phenyl- pyrazolo[1 ,5-a]imidazole, 7-chloro-6-methylpyrazolo[1 ,5-a]imidazole and 7-chloro-6- methylpyrazolo[1 ,5-a]benzimidazole, and the addition salts thereof with an acid.
Preferably, the pyrazolo[5,1-e]pyrazoles are chosen from 8-amino-4-methylpyrazolo[5,1- e]pyrazole and 8-amino-5-chloro-4-methylpyrazolo[5,1-e]pyrazole, and the addition salts thereof with an acid.
Preferably, the pyrazolo[5,1-e]-1 ,2,3-triazoles are chosen from 5-methylpyrazolo[5,1-e]-1 ,2,3- triazole, 5-methyl-6-chloropyrazolo[5,1-e]-1 ,2,3-triazole and 5-phenylpyrazolo[5,1-e]-1 ,2,3- triazole, and the addition salts thereof with an acid. These pyrazoloazoles are described in patent application WO 97/35551 , and the pages in the said prior art patent application devoted to pyrazoloazoles and to their synthesis is incorporated into the present patent application by reference.
As pyrroloazoles that may be used in the compositions according to the present patent application, mention may be made of pyrazolo[1 ,2-b]-1 ,2,4-triazoles, pyrrolo[2,1-c]-1 ,2,4- triazoles, pyrrolo[1 ,2-c]imidazoles, pyrrolo[1 ,2-e]tetrazoles, pyrrolo[1 ,2-a]pyrroles, pyrrolo[1 ,2-a]imidazoles and pyrrolo[1 ,2-c]-1 ,2,3-triazoles.
Preferably, the pyrrolo[1 ,2-b]-1 ,2,4-triazoles are chosen from 3,4-dicyano-8- methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3,4-dicyano-8-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3,4- dicyano-8-tert-butylpyrrolo[1 ,2-b]-1 ,2,4-triazole and 5-chloro-3,4-dicyano-8-methylpyrrolo[1 ,2- b]-1 ,2,4-triazole, and also 5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 5- cyano-4-carboxy-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,5-dicyano-8-methylpyrrolo[1 ,2-b]- 1 ,2,4-triazole, 5-cyano-8-methyl-4-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,8-dimethylpyr- rolo[1 ,2-b]-1 ,2,4-triazole, 4,5-bis(ethoxycarbonyl)-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3- chloro-δ-cyano^-ethoxycarbonyl-δ-methylpyrroloti ,2-b]-1 ,2,4-triazole, 5-cyano-4- ethoxycarbonyl-8-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 5-cyano-4-carboxy-8-phenylpyrrolo[1 ,2- b]-1 ,2,4-triazole, 4,5-dicyano-8-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,5-bis(ethoxycarbonyl)-8- phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, S-chloro-δ-cyano^-ethoxycarbonyl-δ-phenylpyrroloti ,2- b]-1 ,2,4-triazole and 4-cyano-5-carboxy-8-(2-nitro-5-hydroxyphenyl)pyrrolo[1 ,2-b]-1 ,2,4- triazole, and the addition salts thereof with an acid.
Preferably, the pyrrolo[2,1-c]-1 ,2,4-triazoles are chosen from 5,6-dicyano-3- methylpyrrolo[2,1-c]-1 ,2,4-triazole and /-chloro-δ.δ-dicyano-S-methylpyrroloP.I-cl-i ,2,4- triazole, and also 6,7-dicyano-3-methylpyrrolo[2,1-c]-1 ,2,4-triazole, 5-chloro-6,7-dicyano-3- methylpyrrolo[2,1-c]-1 ,2,4-triazole, 6,7-bis(ethoxycarbonyl)-3-methylpyrrolo[2,1-c]-1 ,2,4- triazole, 7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]-1 ,2,4-triazole and 7-cyano-3-methyl-6-tert- butylpyrrolo[2,1-c]-1 ,2,4-triazole, and the addition salts thereof with an acid.
Preferably, the pyrrolo[1 ,2-c]imidazoles are chosen from 6,8-dicyano-5- ethoxycarbonylpyrrolo[1 ,2-c]imidazole and 4-chloro-6,8-dicyano-5-ethoxycarbonylpyrrolo[1 ,2- c]imidazole, and the addition salts thereof with an acid.
Preferably, the pyrrolo[1 ,2-e]tetrazoles are chosen from 6,7-dicyanopyrrolo[1 ,2-e]tetrazole, 6- cyano-7-ethoxycarbonylpyrrolo[1 ,2-e]tetrazole and 5-chloro-6,7-dicyanopyrrolo[1 ,2- e]tetrazole, and the addition salts thereof with an acid.
Preferably, the pyrrolo[1 ,2-a]imidazoles are chosen from 2,3,7-tricyano-6-methylpyrrolo[1 ,2- a]imidazole, 2,3,7-tricyano-6-trifluoromethylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6-tert- butylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6-phenylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6- ethoxycarbonylpyrrolo[1 ,2-a] imidazole, 5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1 ,2-a]imid- azole, 5-chloro-2,3,7-tricyano-6-phenylpyrrolo[1 ,2-a]imidazole, 7-cyano-6- ethoxycarbonylpyrrolo [1 ,2-a]benzimidazole, 7-cyano-6-phenylpyrrolo[1 ,2-a]benzimidazole and 7-amido-6-ethoxycarbonylpyrrolo[1 ,2-a]benzimidazole, and the addition salts thereof with an acid.
Preferably, the pyrrolo[1 ,2-c]-1 ,2,3-triazoles are chosen from 5,6,8-tricyanopyrrolo[1 ,2-c]- 1 ,2,3-triazole, 5,8-tricyano-6-ethoxycarbonylpyrrolo[1 ,2-c]-1 ,2,3-triazole and 4-chloro-5,8- dicyano-6-ethoxycarbonylpyrrolo[1 ,2-c]-1 ,2,3-triazole, and the addition salts thereof with an acid.
These pyrroloazoles are especially described in the following patents and patent applications: US 5 256 526, EP-A-557 851 , EP-A-578 248, EP-A-518 238, EP-A-456 226, EP-A-488 909, EP-A-488 248 and WO 97/35554, and in the following publications: - D. R. Liljegren, Ber. 1964, 3436;
- E.J. Browne, J.C.S., 1962, 5149;
- P. Magnus, J.A.C.S., 1990, 1 12, 2465;
- P. Magnus, J.A.C.S., 1987, 109, 2711 ;
- Angew. Chem. 1960, 72, 956; - and Rec. Trav. Chim. 1961 , 80, 1075; the teachings of which form an integral part of the present patent application.
Among the imidazoloazole derivatives mention may be made more particularly of the compounds described in the following patent applications and patents: US 5 441 863; JP 62- 279 337; JP 06-236 011 and JP 07-092 632, the teachings of which form an integral part of the present patent application.
Imidazoloazole derivatives that may be mentioned most particularly are:
- 7,8-dicyanoimidazolo[3,2-a]imidazole, - 7,8-dicyano-4-methylimidazolo[3,2-a]imidazole, and the addition salts thereof with an acid. Among the pyrazolopyrimidine derivatives mention may be made more particularly of the compounds described in the following patent application: EP-A-304 001 , the teaching of which forms an integral part of the present patent application.
Pyrazolopyrimidine derivatives that may be mentioned most particularly are:
- pyrazolo[1 ,5-a]pyrimidin-7-one,
- 2,5-dimethylpyrazolo[1 ,5-a]pyrimidin-7-one,
- 2-methyl-6-ethoxycarbonylpyrazolo[1 ,5-a]pyrimidin-7-one,
- 2-methyl-5-methoxymethylpyrazolo[1 ,5-a]pyrimidin-7-one, - 2-tert-butyl-5-trifluoromethylpyrazolo[1 ,5-a]pyrimidin-7-one,
- 2,7-dimethylpyrazolo[1 ,5-a]pyrimidin-5-one, and the addition salts thereof with an acid.
As hydroxypyrazolopyrimidine derivatives that are used in the compositions according to the present patent application, mention may be made of hydroxypyrazolo[1 ,5-a]pyrimidines and more particularly 2-hydroxy-5-methyl-7-ethylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-5,6,7- trimethylpyrazolo[1 ,5-a] pyrimidine, 2-hydroxy-5,7-dimethyl-6-ethylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-7-methylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-5-methyl-7-carboxypyrazolo[1 ,5- a]pyrimidine and 2,7-dihydroxy-5,6-dimethylpyrazolo[1 ,5-a]pyrimidine. These hydroxypyrazolopyrimidines are described in patent application DE 4029324, and the passage in the said prior art patent application devoted to hydroxypyrazolopyrimidines and to their synthesis is incorporated into the present patent application by reference.
Among the pyrazoline-3,5-dione derivatives mention may be made more particularly of the compounds described in the following patent applications and patents: JP 07-036 159, JP 07-084 348 and US 4 128 425, and in the following publications:
- L. Wyzgowska, Acta. Pol. Pharm. 1982, 39 (1-3), 83.
- E. Hannig, Pharmazie, 1980, 35 (4), 231
- M. H. Elnagdi, Bull. Chem. Soc. Jap., 46 (6), 1830, 1973 - G. Cardillo, Gazz. Chim. Ital. 1966, 96, (8-9), 973, the teachings of which form an integral part of the present patent application.
Pyrazoline-3,5-dione derivatives that may be mentioned most particularly are:
- 1 ,2-diphenylpyrazoline-3,5-dione, - 1 ,2-diethylpyrazoline-3,5-dione, and the addition salts thereof with an acid. Among the pyrrolo[3,2-d]oxazole derivatives mention may be made more particularly of the compounds described in patent application JP 07 325 375, the teaching of which forms an integral part of the present patent application.
Among the pyrazolo[3,4-d]thiazole derivatives mention may be made more particularly of the compounds described in patent application JP 07 244 361 and in J. Heterocycl. Chem. 16, 13, (1979).
Among the thiazoloazole S-oxide and thiazoloazole S,S-dioxide derivatives that can be used as heterocyclic couplers in the ready-to-use dye composition in accordance with the invention, mention may be made more particularly of the compounds described in the following documents:
- JP 07 09 84 89;
- Khim. Geterotsilk. Soedin, 1967, p. 93; - J. Prakt. Chem., 318, 1976, p. 12;
- Indian J. Heterocycl. Chem. 1995, 5 (2), p. 135;
- Acta. Pol. Pharm. 1995, 52 (5), 415;
- Heterocycl. Commun. 1995, 1 (4), 297;
- Arch. Pharm. (Weinheim, Ger.), 1994, 327 (12), 825.
Carbazole derivatives that may be mentioned include 1 ,3,6,8-tetraaminocarbazole, 1 ,3,6,8- tetraamino-9-n-propylcarbazole, 1 ,3,6,8-tetraamino-9-β-hydroxyethylcarbazole and 1 ,3,6,8- tetraamino-9-(2'-N,N-dimethylaminoethyl)carbazole. These compounds are described in patent application DE 2715680, and the passage in the said prior art patent application devoted to carbazoles and to their synthesis is incorporated into the present patent application by reference.
A carbazole that may also be mentioned is 3-aminocarbazole, described in patent application DE 277 496.
Hydroxyindazole derivatives that may be mentioned include the following monohydroxyindazoles: 4-hydroxyindazole, 5-hydroxyindazole, 6-hydroxyindazole, 7- hydroxyindazole, 7-hydroxy-1-methylindazole, 4-hydroxy-6-methylindazole, 7-hydroxy-6- methylindazole, 7-hydroxy-4,6-dimethylindazole, 6-hydroxy-7-bromoindazole, 6-hydroxy-7- chloroindazole and 6-hydroxy-5,7-dichloroindazole. These hydroxyindazoles are described in patent application DE 26 23 564, and the passage in the said prior art patent application devoted to hydroxyindazoles and to their synthesis is incorporated into the present patent application by reference.
Benzoxazole derivatives that may be mentioned include the following diaminobenzoxazoles: 5,7-diaminobenzoxazole, 5,7-diamino-2-methylbenzoxazole, 5,7-diamino-2- ethylbenzoxazole, 5,7-diamino-2-butylbenzoxazole, 5-dimethylamino-7-aminobenzoxazole, 5-amino-7-diethylaminobenzoxazole and 4,6-diaminobenzoxazole.
These benzoxazoles are described in patent application DE 27 19 424, and the passage in the said prior art patent application devoted to benzoxazoles and to their synthesis is incorporated into the present patent application by reference.
As imidazoloazole derivatives that are used in the compositions according to the present invention, mention may be made of imidazolo[3,2-a]imidazoles, imidazolo[1 ,2-b]-1 ,2,4- triazoles and imidazolo[2,1-c]-1 ,2,4-triazoles.
Preferably, the imidazolo[3,2-a]imidazoles are chosen from 7,8-dicyanoimidazolo[3,2- a]imidazole, 7,8-dicyano-4-methylimidazolo[3,2-a] imidazole, 7,8-dicyano-4- ethylimidazolo[3,2-a]imidazole, 7,8-dicyano-4-isopropylimidazolo[3,2-a]imidazole, 7,8- dicyano-4-phenylimidazolo[3,2-a]imidazole, 5-chloro-7,8-dicyano-4-methylimidazolo[3,2- a]imidazole and 7,8-dicyano-4-trifluoromethylimidazolo[3,2-a]imidazole, and the addition salts thereof with an acid.
Preferably, the imidazolo[1 ,2-b]-1 ,2,4-triazoles are chosen from imidazolo[1 ,2-b]-1 ,2,4- triazole, 6-methylimidazolo[1 ,2-b]-1 ,2,4-triazole, 6-isopropylimidazolo-[1 ,2-b]-1 ,2,4-triazole,
6-phenylimidazolo[1 ,2-b]-1 ,2,4-triazole, 2,6-dimethylimidazolo[1 ,2-b]-1 ,2,4-triazole, 6- isopropyl-2-methylimidazolo[1 ,2-b]-1 ,2,4-triazole, 2-methyl-6-phenylimidazolo[1 ,2-b]-1 ,2,4- triazole, 6-methyl-2-phenylimidazolo[1 ,2-b]-1 ,2,4-triazole, 6-isopropyl-2-phenylimidazolo[1 ,2- b]-1 ,2,4-triazole, 7-chloro-2,6-dimethylimidazolo[1 ,2-b]-1 ,2,4-triazole, 7-chloro-2-phenyl-6- tert-butylimidazolo[1 ,2-b]-1 ,2,4-triazole and 6-trifluoromethyl-imidazolo[1 ,2-b]-1 ,2,4-triazole.
Preferably, the imidazolo[2,1-c]-1 ,2,4-triazoles are chosen from imidazolo[2,1-c]-1 ,2,4- triazole, 5-methylimidazolo[2,1-c]-1 ,2,4-triazole, 5,8-dimethylimidazolo[2,1-c]-1 ,2,4-triazole, 5-methyl-8-phenylimidazolo[2,1-c]-1 ,2,4-triazole, 8-phenylimidazolo[2,1-c]-1 ,2,4-triazole and 6-chloro-5,8-dimethylimidazolo[2,1-c]-1 ,2,4-triazole, and the addition salts thereof with an acid. These imidazoloazoles are described in patent application WO 97/35552, and the passage in the said prior art patent application devoted to imidazoloazoles and to their synthesis is incorporated into the present patent application by reference.
The thiazoloazole derivatives are described in patent application FR 2 752 524, and reference may be made to the passage in the said patent application devoted to thiazoloazoles and to their synthesis.
As pyrrolooxazole derivatives used in the compositions according to the present patent application, mention may be made of the compounds described in general in patent application FR 2 752 522. The passages in the said prior art patent application devoted to pyrrolooxazoles and to their synthesis are incorporated into the present patent application by reference.
As isoxazolone derivatives that are used in the compositions according to the present patent application, mention may be made of 4-carboxy-β:γ-benzisoxazolone, 1-acetyl-4-carboxy- β:γ-benzisoxazolone, 6-carboxy-β:γ-benzisoxazolone, 1-acetyl-6-carboxy-β:γ- benzisoxazolone, β:γ-benzisoxazolone, 1-acetyl-β:γ-benzisoxazolone, 4-methyl-β:γ- benzisoxazolone, 1-acetyl-4-(β-hydroxyethylamino)carbonyl-β:γ-benzisoxazolone, 3-phenyl- 5-isoxazolone, 2-acetyl-3-phenyl-5-isoxazolone, 3,4-diphenyl-5-isoxazolone, 3-methyl-5- isoxazolone and 3,4-tetramethylene-5-isoxazolone. These isoxazolones are described in patent application FR 2 040 260, and the passage in the said prior art patent application devoted to isoxazolones and to their synthesis is incorporated into the present patent application by reference.
As indazolone derivatives that are used in the compositions according to the present patent application, mention may be made of indazolone, 5-chloroindazolone, 6-chloroindazolone, 1- ethylindazolone, 5-dimethylaminoindazolone, 1-methylindazolone, 1-isopropylindazolone, 1- butylindazolone, 3-chloroindazolone, 4-chloroindazolone, 5-methylindazolone, 6- methylindazolone, 5-ethylindazolone, 6-propylindazolone, 5-butylindazolone, 1 ,5- dimethylindazolone, 1 ,6-dimethylindazolone, 1-methyl-5-chloroindazolone, 1-methyl-6- chloroindazolone, 1-ethyl-5-chloroindazolone, 1-ethyl-6-bromoindazolone, 5- aminoindazolone, 6-dimethylaminoindazolone, 5-diethylaminoindazolone, 1-methyl-5- dimethylaminoindazolone, 5-dibutylaminoindazolone and 1-ethyl-5-dipropylaminoindazolone.
These indazolones are described in patent application DE 26 32 390, and the passage in the said prior art patent application devoted to indazolones and to their synthesis is incorporated into the present patent application by reference.
Indole derivatives that may be mentioned include the compounds of formulae (XII) and (XIII) below, or the addition salts thereof with an acid:
Figure imgf000043_0001
(Xi I) (XIIl) in which:
R13 represents a hydrogen atom, a CrC4 alkyl radical or a CrC4 hydroxyalkyl radical;
Ri4 and Ri5, which may be identical or different, represent a hydrogen atom or a d-C4 alkyl, carboxyl or (Ci-C4)alkoxycarbonyl radical;
X represents a hydrogen or halogen atom or a CrC4 alkyl, Ci-Ci8 alkoxy or acetylamino radical;
Ri6 and Ri7, which may be identical or different, represent a hydrogen atom or a Ci-C4 alkyl radical; Ri8 represents a hydrogen atom or a CrC4 alkyl or hydroxyl radical;
Y represents a hydroxyl radical or NHRi9 in which Ri9 represents a hydrogen atom or a d-
C4 alkyl or CrC4 hydroxyalkyl radical; with the proviso that:
- when Ri8 denotes hydroxyl, then it occupies position 6 or 7, - when Y denotes amino, then it occupies position 4, 6 or 7.
Indole derivatives that may be mentioned most particularly include 6-hydroxyindole, 4- hydroxy-1 N-β-hydroxyethylindole and 5,6-dihydroxyindole, and the addition salts thereof with an acid.
lndoline derivatives that may be mentioned most particularly include 6-hydroxyindoline, 6- aminoindoline and 5,6-dihydroxyindoline, and the addition salts thereof with an acid.
Quinoline derivatives that may be mentioned include the compounds of formula (XIV) below, and the addition salts thereof with an acid:
Figure imgf000044_0001
in which Rig denotes a hydroxyl or CrC4 alkoxy radical and R20 denotes a hydrogen atom or an amino radical.
In one preferred variant of the invention, the nitrogenous heterocycles comprise, among the ring members constituting the rings, only nitrogen atoms as heteroatoms in addition to the carbon atoms.
Preferably, the nitrogenous heterocyclic couplers of the invention are chosen from pyridines, indoles and indolines.
The nitrogenous heterocyclic coupler(s) each represent(s) from 0.0001 % to 12% by weight approximately relative to the total weight of the composition according to the invention, and preferably from 0.005% to 6% by weight relative to the total weight of the composition.
The compositions of the invention may contain one or more additional couplers other than the nitrogenous heterocyclic couplers of the invention.
The additional 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 non-nitrogenous heterocyclic couplers, for instance sesamol and derivatives thereof, and the addition salts thereof with an acid.
These additional 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 and α-naphthol, and the addition salts thereof with an acid.
When they are present, the additional 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. 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.
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 CrC4 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:
N-W -N {XV}
in which w is a propylene residue optionally substituted with a hydroxyl group or a CrCβ alkyl radical; R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom or a C-i-Cδ alkyl or CrCβ hydroxyalkyl radical. In addition to the direct dye(s) of the invention defined above, the dye compositions in accordance with the invention may contain one or more other 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 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) of formula (I) with a composition containing at least one oxidation base and at least one nitrogenous heterocyclic coupler as defined above.
When it is ready-to-use, 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 one particular embodiment, 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 optionally a composition (C1 ) in a suitable dyeing medium, and then in mixing together at the time of use compositions (A1 ) and (B1 ) and optionally (C1 ), followed by applying this mixture to keratin fibres, composition (A1 ) and/or composition (C1 ) containing at least one oxidation base and at least one nitrogenous heterocyclic coupler 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 ) as defined above, a second compartment contains composition (B1 ), and optionally a third compartment contains composition (C1 ) 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 imgf000047_0001
Application Examples
Example 1
The dye composition below was prepared (amounts expressed as grams of active material):
Figure imgf000047_0002
At the time of use, this composition is mixed weight for weight with 20-volumes aqueous hydrogen peroxide solution at pH 3. The mixture is 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 (20°C).
After the action time, the locks are rinsed, shampooed and then rinsed and dried. They are dyed in a sparingly selective chromatic violet-blond shade.
Example 2
If dye 1 is replaced weight for weight with dye 2 and the coupler 2-amino-3-hydroxypyridine is replaced with 6-hydroxyindole, a sparingly selective chromatic violet-coppery blond shade is finally obtained.

Claims

1. Composition for dyeing keratin fibres, comprising, in a suitable dyeing medium, at least one oxidation base, at least one nitrogenous heterocyclic coupler and at least one tetraazapentamethine compound of formula I
Figure imgf000049_0001
in which
W1 represents a cationic heteroaromatic radical of formula (II) or (III):
Figure imgf000049_0002
- W2 represents a heteroaromatic radical of formula (IV) or (V):
Figure imgf000049_0003
OV) 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 CR1O,
- Z3 represents a nitrogen atom or a radical CR11,
- 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 Z11 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, R1O 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, R9, R15, R21 and R22 represent, independently of each other, a linear or branched C1-Cs 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, R11, R12, Ri3, Ri4, Ri7, R18, 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 (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, R8, Rn, Ri2, R13, R14, R17, R18, R19 and R20 do not comprise a peroxide bond or diazo or nitroso radicals,
- R2 with R10, Rn 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.
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 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 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 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 R16 represent a hydrogen atom, a C1-C4 alkyl radical, which is unsubstituted or substituted with one or two radicals chosen from hydroxyl, amino, C1-C2 (di)alkylamino and carboxyl radicals, or a phenyl radical.
6. Composition according to any one of the preceding claims, in which R2, R6, R10 and R16 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 R1, R4, R5, R7, Rg, R15, R21 and R22 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, R21 and R22 represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2- carboxyethyl or 2-sulfonylethyl radical.
9. Composition according to any one of the preceding claims, in which R3, R8, R11, R12, R-13, R14, R17, R-I8, R-19 and R2o 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, Ri3, Ri4, Ri7, 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.
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-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-dimethylamino-phenyl)-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 W1 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-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.
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-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 - 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 W1 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-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.
21. Composition according to any one of Claims 1 to 10, in which W1 is a 2- benzimidazolium radical and W2 is a 4-pyridine 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-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.
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- 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. 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-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. 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 oxidation base(s) is (are) chosen from para-phenylenediamines, bis(phenyl)- alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
31. Composition according to the preceding claim, characterized in that the para- phenylenediamines are chosen from the para-phenylenediamines of formula (Vl) below, and the addition salts thereof with an acid:
Figure imgf000065_0001
NH2 in which:
Ri represents a hydrogen atom, a CrC4 alkyl radical, a d-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a (Ci-C4)alkoxy(Ci-C4)alkyl radical, a CrC4 alkyl radical substituted with a nitrogenous group, a phenyl group or a 4'-aminophenyl group;
R2 represents a hydrogen atom, a CrC4 alkyl radical, a CrC4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a (Ci-C4)alkoxy(CrC4)alkyl radical or a CrC4 alkyl radical substituted with a nitrogenous group;
Ri 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 C1-C4 alkyl radical, a sulfo radical, a carboxy radical, a C1-C4 monohydroxyalkyl radical, a C1-C4 hydroxyalkoxy radical, an acetylamino(CrC4)alkoxy radical, a C1-C4 mesylaminoalkoxy radical or a carbamoylamino(Ci-C4)alkoxy radical,
R4 represents a hydrogen or halogen atom or a CrC4 alkyl radical.
32. Composition according to the preceding claim, characterized in that the nitrogenous groups of formula (Vl) are chosen from amino, mono(Ci-C4)alkylamino, di(Ci-C4)alkylamino, tri(Ci-C4)alkylamino, monohydroxy(Ci-C4)alkylamino, imidazolinium and ammonium radicals.
33. Composition according to any one of the preceding claims, characterized in that the oxidation base is chosen from para-phenylenediamine, para-tolylenediamine, 2-chloro-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-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.
34. Composition according to the preceding claim, characterized in that the para- phenylenediamines are chosen from para-phenylenediamine, para-tolylenediamine, 2- isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxy- ethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para- phenylenediamine and 2-chloro-para-phenylenediamine, and the addition salts thereof with an acid.
35. Composition according to any one of the preceding claims, characterized in that the oxidation base is chosen from the compounds corresponding to formula (VII) below, and the addition salts thereof with an acid:
Figure imgf000066_0001
in which: - Z1 and Z2, which may be identical or different, represent a hydroxyl or -NH2 group that may be substituted with a d-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; - Rj, RS, Rg, R1O, Rn and R12, 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 (VII) contain only one linker arm Y per molecule.
36. Composition according to the preceding claim, characterized in that the nitrogenous groups of formula (VII) are chosen from amino, mono(C1-C4)alkylamino, di(CrC4)alkylamino, tri(CrC4)alkylamino, monohydroxy(CrC4)alkylamino, imidazolinium and ammonium radicals.
37. Composition according to any one of the preceding claims, characterized in that the oxidation base is chosen from N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3- diaminopropanol, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, 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-diamino- phenoxy)-3,5-dioxaoctane, and the addition salt thereof with an acid are particularly preferred. 38. Composition according to the preceding claim, characterized in that the oxidation base is chosen from N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol and 1 ,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or an addition salt thereof with an acid are particularly preferred. 39. Composition according to any one of the preceding claims, characterized in that the oxidation base is chosen from the para-aminophenols corresponding to formula (VIII) below, and the addition salts thereof with an acid:
Figure imgf000067_0001
NH. in which: R13 represents a hydrogen atom, a halogen atom such as fluorine, a C1-C4 alkyl, Ci-C4 monohydroxyalkyl, (Ci-C4)alkoxy(Ci-C4)alkyl, d-C4 aminoalkyl or hydroxy(Ci-C4)alkylamino(Ci-C4)alkyl radical,
Ri4 represents a hydrogen atom or a halogen atom such as fluorine, a CrC4-alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, CrC4 aminoalkyl, CrC4 cyanoalkyl or (C1-C4)alkoxy(C1-C4)alkyl radical.
40. Composition according to the preceding claim, characterized in that the oxidation base is chosen from 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.
41. Composition according to any one of the preceding claims, characterized in that the oxidation base is an ortho-aminophenol chosen 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.
42. Composition according to any one of the preceding claims, characterized in that the oxidation base is a heterocyclic base chosen from pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and the addition salts thereof with an acid.
43. Composition according to the preceding claim, characterized in that the oxidation base is chosen from 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3- diamino-6-methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4- diaminopyridine, and the addition salts thereof with an acid.
44. Composition according to Claim 42, characterized in that the oxidation base is chosen from 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy- 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, 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-hydroxyethyl)amino]ethanol;
2-[(7-aminopyrazolo[1 ,5-a]pyrimidin-3-yl)(2-hydroxyethyl)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.
45. Composition according to Claim 42, characterized in that the oxidation base is chosen from pyrazole derivatives, for instance 4,5-diamino-1-methylpyrazole, 3,4- diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3-dimethylpyrazole, 4,5-diamino-3-methyl-1 -phenylpyrazole, 4,5-diamino-1 -methyl-3-phenylpyrazole, 4-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-i-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.
46. Composition according to any one of the preceding claims, characterized in that the oxidation base(s) represent(s) from 0.0005% to 12% by weight approximately relative to the total weight of the dye composition, and even more preferentially from 0.005% to 6% by weight approximately relative to this weight.
47. Composition according to any one of the preceding claims, characterized in that the nitrogenous heterocyclic coupler is chosen from pyridine derivatives, benzimidazole derivatives, benzomorpholine derivatives, pyrazoloazole derivatives, pyrroloazole derivatives, imidazoloazole derivatives, pyrazolopyrimidine derivatives, hydroxypyrazolo- pyrimidine derivatives, pyrazoline-3,5-dione derivatives, pyrrolo[3,2-d]oxazole derivatives, pyrazolo[3,4-d]thiazole derivatives, thiazoloazole S-oxide derivatives, thiazoloazole S1S- dioxide derivatives, carbazole derivatives, hydroxyindazole derivatives, benzoxazole derivatives, thiazoloazole derivatives, imidazoloazole derivatives, isoxazolone derivatives, indazolone derivatives, indole derivatives, indoline derivatives and quinoline derivatives, and the addition salts thereof with an acid.
48. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic couplers are chosen from the compounds of formula (IX) below, and the addition salts thereof with an acid:
Figure imgf000069_0001
in which:
Ru represents a hydrogen atom, a hydroxyl, d-C4 alkoxy, CrC4 monohydroxyalkoxy, C2-C4 polyhydroxyalkoxy, amino, C1-C4 mono- or dialkylamino, C1-C4 mono- or di(hydroxyalkyl)amino radical or the group -OCH2CH2COCH2CH2OH, R-I5 and R17, which may be identical or different, represent a hydrogen atom or a hydroxyl, amino or CrC4 alkyl radical, R16 represents a hydrogen atom or a C1-C4 alkyl radical,
R18 represents a hydrogen atom or a hydroxyl, C1-C4 alkoxy, C1-C4 monohydroxyalkoxy, C2- C4 polyhydroxyalkoxy or amino radical; at least two of the substituents R14 to R18 being other than hydrogen and two para substituents not possibly denoting an amino or substituted amino group. 49. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic coupler is chosen from 2-amino-3-hydroxypyridine, 2,6-dihydroxy-4- methylpyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6- bis(β-hydroxyethyl)oxy-3,5-diaminopyridine, 3-amino-2,6-dimethoxy-5-hydroxypyridine, 2,6- diaminopyridine, 3-oxo-5-(3',5'-diamino-2'-pyridyloxy)pentanol and 3-(3',5'-diamino-2'- pyridyloxy)-2-hydroxypropanol, and the addition salts thereof with an acid.
50. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from the benzimidazole derivatives of formula (X) below, and the addition salts thereof with an acid:
Figure imgf000070_0001
in which:
R5 represents a hydrogen atom or a C1-C4 alkyl radical,
Re represents a hydrogen atom or a C1-C4 alkyl or phenyl radical,
R7 represents a hydroxyl, amino or methoxy radical,
R8 represents a hydrogen atom or a hydroxyl, methoxy or C1-C4 alkyl radical; with the proviso that:
- when R7 denotes an amino radical, then it occupies position 4,
- when R7 occupies position 4, then R8 occupies position 7,
- when R7 occupies position 5, then R8 occupies position 6.
51. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic coupler is chosen from 4,7-dihydroxybenzimidazole, 4,7-dihydroxy-1- methylbenzimidazole, 4,7-dihydroxy-2-methylbenzimidazole, 4,7-dihydroxy-1 -ethylbenzimid- azole, 4,7-dihydroxy-1-propylbenzimidazole, 4,7-dihydroxy-1-butylbenzimidazole, 4,7- dihydroxy-2-ethylbenzimidazole, 4,7-dihydroxy-2-butylbenzimidazole, 4,7-dihydroxy-1 ,2- dimethylbenzimidazole hydrobromide, 4,7-dimethoxybenzimidazole, 4,7-dimethoxy-1- methylbenzimidazole, 4,7-dimethoxy-1 -ethylbenzimidazole, 4,7-dimethoxy-2- methylbenzimidazole, 4,7-dimethoxy-2-ethylbenzimidazole, 5,6-dihydroxybenzimidazole, 5,6- dihydroxy-1-methylbenzimidazole, 5, 6-dihydroxy-1 -ethylbenzimidazole, 5,6-dihydroxy-1- butylbenzimidazole, 5,6-dihydroxy-2-methylbenzimidazole, 5,6-dihydroxy-2-butyl- benzimidazole, 5,6-dihydroxy-2-phenylbenzimidazole hydrobromide, 5,6- dimethoxybenzimidazole, 5,6-dimethoxy-1-methylbenzimidazole, 5, 6-dimethoxy-1 -ethylbenzimidazole, 5,6-dimethoxy-1-propylbenzimidazole, 5,6-dimethoxy-2-methylbenzimidazole, 5,6- dimethoxy-2-butylbenzimidazole, 5,6-dimethoxy-2-phenylbenzimidazole, 5,6-dimethoxy-1 ,2- dimethylbenzimidazole, 4-hydroxy-7-methoxybenzimidazole, 5-hydroxy-6- methoxybenzimidazole, 4-hydroxy-7-methoxy-1-methylbenzimidazole, 5-hydroxy-6-methoxy- 1 ,2-dimethylbenzimidazole and 5-amino-1 -methyl-2-(ω-cyanoacetyl)benzimidazole. 52. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from the benzomorpholine derivatives of formula (Xl) below, and the addition salts thereof with an acid:
Figure imgf000071_0001
in which:
R9 and R10, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical, Z represents a hydroxyl or amino radical.
53. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic coupler is chosen from 6-hydroxy-1 ,4-benzomorpholine, N-methyl-6-hydroxy- 1 ,4-benzomorpholine and 6-amino-1 ,4-benzomorpholine, and the addition salts thereof with an acid. 54. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from pyrazolo[1 ,5-b]-1 ,2,4-triazoles, pyrazolo[3,2-c]-1 ,2,4-triazoles, pyrazolotetrazoles, pyrazolo[1 ,5-a]imidazoles, pyrazolo[1 ,5-e]pyrazoles and pyrazolo[1 ,5-e]- 1 ,2,3-triazoles. 55. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic coupler is chosen from 2-methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2- ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-phenylpyra- zolo[1 ,5-b]-1 ,2,4-triazole, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2- ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6- methyl-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-methylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-carboxy-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-isopropylpyrazolo[1 ,5- b]-1 ,2,4-triazole, 6-carboxy-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2- methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl- 2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6- amino-2-methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-amino-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-amino-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-amino-2-phenylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-ethylthio-2-methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethylthio-2-ethylpyrazolo[1 ,5-b]- 1 ,2,4-triazole, 6-ethylthio-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethylthio-2- phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethoxy-2-methylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6- ethoxy-2-ethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethoxy-2-isopropylpyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-ethoxy-2-phenylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2-(2'- aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-(2'-aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4- triazole, 6-phenyl-2-(2'-aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-ethylthio-2-(2'-amino- ethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-(2'-aminoethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 2-(2'- hydroxyethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-methyl-2-(2'-hydroxyethyl)pyrazolo[1 ,5-b]-
1 ,2,4-triazole, 6-ethylthio-2-(2'-hydroxyethyl) pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-carboxy-2-(2'- hydroxyethyl)pyrazolo[1 ,5-b]-1 ,2,4-triazole, 6-phenyl-2-(2'-hydroxyethyl)pyrazolo[1 ,5-b]-
1 ,2,4-triazole, 7-chloro-2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole and 7-bromo-2,6-dimethyl pyrazolo[1 ,5-b]-1 ,2,4-triazole, and the addition salts thereof with an acid. 56. Composition according to Claim 54, characterized in that the nitrogenous heterocyclic coupler is chosen from 3-methylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-methylsulfinyl-6- phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-isopropyl- pyrazolo[3,2-c]-1 ,2,4-triazole, 3-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 3-(2'- aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 3-(2'-hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6- methyl-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 3,6-dimethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6- methyl-3-isopropyl pyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-phenylpyrazolo[3,2-c]-1 ,2,4- triazole, 6-methyl-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-(2'- hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-methyl-3-methylthiopyrazolo[3,2-c]-1 ,2,4- triazole, 6-phenyl-3-methylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3-ethylpyrazolo[3,2-c]- 1 ,2,4-triazole, 6-isopropyl-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3- isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3-phenyl pyrazolo[3,2-c]-1 ,2,4-triazole, 6- phenyl-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-phenyl-3-(2'-hydroxyethyl)pyrazolo- [3,2-c]-1 ,2,4-triazole, 6-phenyl-3-methylthiopyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3- methylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6- ethylthio-3-isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3-phenylpyrazolo[3,2-c]-1 ,2,4- triazole, 6-ethylthio-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-ethylthio-3-(2'- hydroxyethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-trifluoromethyl-3-methylthiopyrazolo[3,2-c]- 1 ,2,4-triazole, 6-trifluoromethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3-methylpyrazolo[3,2- c]-1 ,2,4-triazole, 6-carboxy-3-ethylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3- isopropylpyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3-phenylpyrazolo[3,2-c]-1 ,2,4-triazole, 6- carboxy-3-(2'-aminoethyl)pyrazolo[3,2-c]-1 ,2,4-triazole, 6-carboxy-3-(2'- hydroxyethyl)pyrazolo [3,2-c]-1 ,2,4-triazole, 7-chloro-3,6-dimethylpyrazolo[3,2-c]-1 ,2,4- triazole and 7-methoxycarbonyl-3,6-dimethylpyrazolo[3,2-c]-1 ,2,4-triazole, and the addition salts thereof with an acid.
57. Composition according to Claim 54, characterized in that the nitrogenous heterocyclic coupler is chosen from pyrazolo[5,1-e]tetrazole, 6-methylpyrazolo[5,1-e]tetrazole, 6- phenylpyrazolo[5,1-e]tetrazole, 6-carboxypyrazolo[5,1-e]tetrazole and 7-chloro-6-methylpyra- zolo[5,1-e]tetrazole, and the addition salts thereof with an acid.
58. Composition according to Claim 54, characterized in that the nitrogenous heterocyclic coupler is chosen from pyrazolo[1 ,5-a]imidazole, 2-methylpyrazolo[1 ,5-a]imidazole, 2- phenylpyrazolo[1 ,5-a]imidazole, pyrazolo[1 ,5-a]benzimidazole, 6-methylpyrazolo[1 ,5-a]- imidazole, 2,6-dimethylpyrazolo[1 ,5-a]imidazole, 6-methyl-2-phenylpyrazolo[1 ,5-a]imidazole, 6-methylpyrazolo[1 ,5-a]benzimidazole, 6-phenylpyrazolo[1 ,5-a]imidazole, 6-phenyl-2- methylpyrazolo [1 ,5-a]imidazole, 2,6-diphenylpyrazolo[1 ,5-a]imidazole, 6-phenylpyrazolo[1 ,5- a]benzimidazole, 6-carboxypyrazolo[1 ,5-a]imidazole, 6-carboxy-2-methylpyrazolo[1 ,5- a]imidazole, 6-carboxy-2-phenylpyrazolo[1 ,5-a]imidazole, 6-carboxypyrazolo[1 ,5- a]benzimidazole, 6-ethoxypyrazolo[1 ,5-a]imidazole, 6-ethoxy-2-methylpyrazolo[1 ,5- a]imidazole, 6-ethoxy-2-phenylpyrazolo[1 ,5-a]imidazole, 6-trifluoromethylpyrazolo[1 ,5- a]benzimidazole, 6-aminopyrazolo[1 ,5-a]imidazole, 6-amino-2-methylpyrazolo[1 ,5-a]imid- azole, 6-amino-2-phenyl pyrazolo[1 ,5-a]imidazole, 6-aminopyrazolo[1 ,5-a]benzimidazole, 6- ethylthiopyrazolo[1 ,5-a]imidazole, 6-ethylthio-2-methylpyrazolo[1 ,5-a]imidazole, 6-ethylthio-2- phenylpyrazolo[1 ,5-a]imidazole, 7-chloro-6-methylpyrazolo[1 ,5-a]imidazole and 7-chloro-6- methylpyrazolo[1 ,5-a]benzimidazole, and the addition salts thereof with an acid.
59. Composition according to Claim 54, characterized in that the nitrogenous heterocyclic coupler is chosen from 8-amino-4-methylpyrazolo[5,1-e]pyrazole and 8-amino-5-chloro-4- methylpyrazolo[5,1-e]pyrazole, and the addition salts thereof with an acid.
60. Composition according to Claim 54, characterized in that the nitrogenous heterocyclic coupler is chosen from 5-methylpyrazolo[5,1-e]-1 ,2,3-triazole, 5-methyl-6-chloropyrazolo[5,1- e]-1 ,2,3-triazole and 5-phenylpyrazolo[5,1-e]-1 ,2,3-triazole, and the addition salts thereof with an acid. 61. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from pyrrolo[1 ,2-b]-1 ,2,4-triazoles, pyrrolo[2,1-c]-1 ,2,4-triazoles, pyrrolo[1 ,2-c]imidazoles, pyrrolo[1 ,2-e]tetrazoles, pyrrolo[1 ,2-a]pyrroles, pyrrolo[1 ,2- a]imidazoles and pyrrolo[1 ,2-c]-1 ,2,3-triazoles.
62. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic coupler is chosen from 3,4-dicyano-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3,4- dicyano-8-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3,4-dicyano-8-tert-butylpyrrolo[1 ,2-b]-1 ,2,4- triazole and 5-chloro-3,4-dicyano-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, and also 5-cyano-4- ethoxycarbonyl-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 5-cyano-4-carboxy-8-methylpyrrolo[1 ,2- b]-1 ,2,4-triazole, 4,5-dicyano-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 5-cyano-8-methyl-4- phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,8-dimethylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,5-di(eth- oxycarbonyl)-8-methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, S-chloro-δ-cyano^-ethoxycarbonyl-δ- methylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 5-cyano-4-ethoxycarbonyl-8-phenylpyrrolo[1 ,2-b]-1 ,2,4- triazole, 5-cyano-4-carboxy-8-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,5-dicyano-8-phenyl- pyrrolo[1 ,2-b]-1 ,2,4-triazole, 4,5-di(ethoxycarbonyl)-8-phenylpyrrolo[1 ,2-b]-1 ,2,4-triazole, 3- chloro-δ-cyano^-ethoxycarbonyl-δ-phenylpyrroloti ,2-b]-1 ,2,4-triazole and 4-cyano-5- carboxy-8-(2-nitro-5-hydroxyphenyl)pyrrolo[1 ,2-b]-1 ,2,4-triazole, and the addition salts thereof with an acid.
63. Composition according to Claim 61 , characterized in that the nitrogenous heterocyclic coupler is chosen from 5, 6-dicyano-3-methylpyrrolo[2,1-c]-1 ,2,4-triazole and 7-chloro-5,6- dicyano-3-methylpyrrolo[2,1-c]-1 ,2,4-triazole, and also 6,7-dicyano-3-methylpyrrolo[2,1-c]- 1 ,2,4-triazole, 5-chloro-6,7-dicyano-3-methylpyrrolo[2,1-c]-1 ,2,4-triazole, 6,7-di(ethoxy- carbonyl)-3-methylpyrrolo[2,1-c]-1 ,2,4-triazole, 7-cyano-3-methyl-6-phenylpyrrolo[2,1-c]- 1 ,2,4-triazole and 7-cyano-3-methyl-6-tert-butylpyrrolo[2,1-c]-1 ,2,4-triazole, and the addition salts thereof with an acid.
64. Composition according to Claim 61 , characterized in that the nitrogenous heterocyclic coupler is chosen from e.δ-dicyano-S-ethoxycarbonylpyrroloπ ^-cJimidazole and 4-chloro- δ.δ-dicyano-δ-ethoxycarbonylpyrroloti ^-climidazole, and the addition salts thereof with an acid.
65. Composition according to Claim 61 , characterized in that the nitrogenous heterocyclic coupler is chosen from 6,7-dicyanopyrrolo[1 ,2-e]tetrazole, 6-cyano-7- ethoxycarbonylpyrrolo[1 ,2-e]tetrazole and 5-chloro-6,7-dicyanopyrrolo[1 ,2-e]tetrazole, and the addition salts thereof with an acid.
66. Composition according to Claim 61 , characterized in that the nitrogenous heterocyclic coupler is chosen from 2,3,7-tricyano-6-methylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6- trifluoromethylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6-tert-butylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6-phenylpyrrolo[1 ,2-a]imidazole, 2,3,7-tricyano-6-ethoxycarbonylpyrrolo[1 ,2- a]imidazole, 5-chloro-2,3,7-tricyano-6-tert-butylpyrrolo[1 ,2-a]imidazole, 5-chloro-2,3,7- tricyano-6-phenylpyrrolo[1 ,2-a]imidazole, 7-cyano-6-ethoxycarbonylpyrrolo[1 ,2-a]benz- imidazole, 7-cyano-6-phenylpyrrolo[1 ,2-a]benzimidazole and 7-amido-6- ethoxycarbonylpyrrolo[1 ,2-a]benzimidazole, and the addition salts thereof with an acid.
67. Composition according to Claim 61 , characterized in that the nitrogenous heterocyclic coupler is chosen from 5,6,8-tricyanopyrrolo[1 ,2-c]-1 ,2,3-triazole, 5,8-dicyano-6- ethoxycarbonylpyrrolo[1 ,2-c]-1 ,2,3-triazole and 4-chloro-5,8-dicyano-6-ethoxycarbonyl- pyrrolo[1 ,2-c]-1 ,2,3-triazole, and the addition salts thereof with an acid.
68. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from - 7,8-dicyanoimidazolo[3,2-a]imidazole,
- 7,8-dicyano-4-methylimidazolo[3,2-a]imidazole, and the addition salts thereof with an acid.
69. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from: - pyrazolo[1 ,5-a]pyrimidin-7-one,
- 2,5-dimethylpyrazolo[1 ,5-a]pyrimidin-7-one,
- 2-methyl-6-ethoxycarbonylpyrazolo[1 ,5-a]pyrimidin-7-one,
- 2-methyl-5-methoxymethylpyrazolo[1 ,5-a]pyrimidin-7-one,
- 2-tert-butyl-5-trifluoromethylpyrazolo[1 ,5-a]pyrimidin-7-one, - 2,7-dimethylpyrazolo[1 ,5-a]pyrimidin-5-one, and the addition salts thereof with an acid.
70. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from 2-hydroxy-5-methyl-7-ethylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy- 5,6,7-trimethylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-5,7-dimethyl-6-ethylpyrazolo[1 ,5-a]pyri- midine, 2-hydroxy-7-methylpyrazolo[1 ,5-a]pyrimidine, 2-hydroxy-5-methyl-7- carboxypyrazolo[1 ,5-a]pyrimidine and 2,7-dihydroxy-5,6-dimethylpyrazolo[1 ,5-a]pyrimidine, and the addition salts thereof with an acid.
71. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from - 1 ,2-diphenylpyrazoline-3,5-dione,
- 1 ,2-diethylpyrazoline-3,5-dione, and the addition salts thereof with an acid.
72. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from 1 ,3,6,8-tetraaminocarbazole, 1 ,3,6,8-tetraamino-9-n-propylcarbazole, 1 ,3,6,8-tetraamino-9-β-hydroxyethylcarbazole, 1 ,3,6,8-tetraamino-9-(2'-N,N-dimethylamino- ethyl)carbazole and 3-aminocarbazole, and the addition salts thereof with an acid.
73. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from: 4-hydroxyindazole, 5-hydroxyindazole, 6-hydroxyindazole, 7- hydroxyindazole, 7-hydroxy-1-methylindazole, 4-hydroxy-6-methylindazole, 7-hydroxy-6- methylindazole, 7-hydroxy-4,6-dimethylindazole, 6-hydroxy-7-bromoindazole, 6-hydroxy-7- chloroindazole and 6-hydroxy-5,7-dichloroindazole, and the addition salts thereof with an acid.
74. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from 5,7-diaminobenzoxazole, 5,7-diamino-2-methylbenzoxazole, 5,7- diamino-2-ethylbenzoxazole, 5,7-diamino-2-butylbenzoxazole, 5-dimethylamino-7-amino- benzoxazole, 5-amino-7-diethylaminobenzoxazole and 4,6-diaminobenzoxazole, and the addition salts thereof with an acid.
75. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from imidazolo[3,2-a]imidazoles, imidazolo[1 ,2-b]-1 ,2,4-triazoles and imidazolo[2,1-c]-1 ,2,4-triazoles. 76. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic coupler is chosen from 7,8-dicyanoimidazolo[3,2-a]imidazole, 7,8-dicyano-4- methylimidazolo[3,2-a]imidazole, 7,8-dicyano-4-ethyl imidazolo[3,2-a]imidazole, 7,8-dicyano- 4-isopropylimidazolo[3,2-a]imidazole, 7,8-dicyano-4-phenylimidazolo[3,2-a]imidazole, 5- chloro-7,8-dicyano-4-methylimidazolo[3,2-a]imidazole and 7,8-dicyano-4- trifluoromethylimidazolo[3,2-a]imidazole, and the addition salts thereof with an acid.
77. Composition according to Claim 75, characterized in that the nitrogenous heterocyclic coupler is chosen from imidazolo[1 ,2-b]-1 ,2,4-triazole, 6-methylimidazolo[1 ,2-b]-1 ,2,4- triazole, 6-isopropylimidazolo[1 ,2-b]-1 ,2,4-triazole, 6-phenylimidazolo[1 ,2-b]-1 ,2,4-triazole, 2,6-dimethylimidazolo[1 ,2-b]-1 ,2,4-triazole, 6-isopropyl-2-methylimidazolo[1 ,2-b]-1 ,2,4- triazole, 2-methyl-6-phenylimidazolo[1 ,2-b]-1 ,2,4-triazole, 6-methyl-2-phenylimidazolo[1 ,2-b]-
1 ,2,4-triazole, 6-isopropyl-2-phenylimidazolo[1 ,2-b]-1 ,2,4-triazole, 7-chloro-2,6- dimethylimidazolo[1 ,2-b]-1 ,2,4-triazole, 7-chloro-2-phenyl-6-tert-butylimidazolo[1 ,2-b]-1 ,2,4- triazole and 6-trifluoromethylimidazolo[1 ,2-b]-1 ,2,4-triazole, and the addition salts thereof with an acid. 78. Composition according to Claim 75, characterized in that the nitrogenous heterocyclic coupler is chosen from imidazolo[2,1-c]-1 ,2,4-triazole, 5-methylimidazolo[2,1-c]-1 ,2,4- triazole, 5,8-dimethylimidazolo[2,1-c]-1 ,2,4-triazole, 5-methyl-8-phenylimidazolo[2,1-c]-1 ,2,4- triazole, 8-phenylimidazolo[2,1-c]-1 ,2,4-triazole and 6-chloro-5,8-dimethylimidazolo[2,1-c]- 1 ,2,4-triazole, and the addition salts thereof with an acid. 79. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from 4-carboxy-β:γ-benzisoxazolone, 1-acetyl-4-carboxy-β:γ-benzisox- azolone, 6-carboxy-β:γ-benzisoxazolone, 1-acetyl-6-carboxy-β:γ-benzisoxazolone, β:γ- benzisoxazolone, 1-acetyl-β:γ-benzisoxazolone, 4-methyl-β:γ-benzisoxazolone, 1-acetyl-4- (β-hydroxy ethylamino)carbonyl-β:γ-benzisoxazolone, 3-phenyl-5-isoxazolone, 2-acetyl-3- phenyl-5-isoxazolone, 3,4-diphenyl-5-isoxazolone, 3-methyl-5-isoxazolone and 3,4- tetramethylene-5-isoxazolone, and the addition salts thereof with an acid.
80. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from 5-chloroindazolone, 6-chloroindazolone, 1-ethylindazolone, 5- dimethylaminoindazolone, 1-methylindazolone, 1-isopropylindazolone, 1-butylindazolone, 3- chloroindazolone, 4-chloroindazolone, 5-methylindazolone, 6-methylindazolone, 5- ethylindazolone, 6-propylindazolone, 5-butylindazolone, 1 ,5-dimethylindazolone, 1 ,6- dimethylindazolone, i-methyl-5-chloroindazolone, 1-methyl-6-chloroindazolone, 1-ethyl-5- chloroindazolone, 1-ethyl-6-bromoindazolone, 5-aminoindazolone, 6-dimethyl- aminoindazolone, 5-diethylaminoindazolone, 1-methyl-5-dimethylaminoindazolone, 5- dibutylaminoindazolone and 1-ethyl-5-dipropylaminoindazolone, and the addition salts thereof with an acid.
81. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from the compounds of formulae (XII) and (XIII) below, or the addition salt thereof with an acid:
Figure imgf000077_0001
in which:
R13 represents a hydrogen atom, a CrC4 alkyl radical or a CrC4 hydroxyalkyl radical;
Ri4 and Ri5, which may be identical or different, represent a hydrogen atom or a d-C4 alkyl, carboxyl or (Ci-C4)alkoxycarbonyl radical;
X represents a hydrogen or halogen atom or a d-C4 alkyl, CrCi8 alkoxy or acetylamino radical;
Ri6 and Ri7, which may be identical or different, represent a hydrogen atom or a d-C4 alkyl radical;
Ri8 represents a hydrogen atom or a CrC4 alkyl or hydroxyl radical;
Y represents a hydroxyl radical or NHR19 in which R19 represents a hydrogen atom or a Cr C4 alkyl or CrC4 hydroxyalkyl radical; with the proviso that:
- when Ri8 denotes hydroxyl, then it occupies position 6 or 7,
- when Y denotes amino, then it occupies position 4, 6 or 7.
82. Composition according to the preceding claim, characterized in that the nitrogenous heterocyclic coupler is chosen from 6-hydroxyindole, 4-hydroxy-1 N-β-hydroxyethylindole and 5,6-dihydroxyindole, and the addition salts thereof with an acid.
83. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from 6-hydroxyindoline, 6-aminoindoline and 5,6-dihydroxyindoline, and the addition salts thereof with an acid.
84. Composition according to Claim 47, characterized in that the nitrogenous heterocyclic coupler is chosen from the quinoline derivatives of formula (XIV) below, and the addition salts thereof with an acid:
Figure imgf000078_0001
in which Rig denotes a hydroxyl or CrC4 alkoxy radical and R20 denotes a hydrogen atom or an amino radical.
85. Composition according to any one of the preceding claims, characterized in that the nitrogenous heterocyclic coupler is chosen from nitrogenous heterocycles comprising, among the ring members constituting the rings, only nitrogen atoms as heteroatoms in addition to the carbon atoms.
86. Composition according to any one of the preceding claims, characterized in that the nitrogenous heterocyclic coupler is chosen from pyridines, indoles and indolines.
87. Composition according to any one of the preceding claims, characterized in that the nitrogenous heterocyclic coupler(s) each represent(s) from 0.0001 % to 12% by weight approximately relative to the total weight of the composition according to the invention, and preferably from 0.005% to 6% by weight relative to the total weight of the composition.
88. Composition according to any one of the preceding claims, characterized in that the composition of the invention contains one or more additional couplers other than the nitrogenous heterocyclic couplers of the invention chosen from meta-aminophenols, meta- phenylenediamines, meta-diphenols, naphthols and non-nitrogenous heterocyclic couplers, and the addition salts thereof with an acid.
90. Composition according to the preceding claim, characterized in that the additional couplers that may be used in the dye composition according to the invention are chosen from 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(β-hydroxy- ethyl)amino-2-methylphenol, 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 and α-naphthol, and the addition salts thereof with an acid.
92. Composition according to any one of the preceding claims, characterized in that it comprises at least one additional direct dye other than the direct dyes of the invention.
94. Composition according to any one of the preceding claims, characterized in that it also comprises an oxidizing agent.
95. Dyeing process comprising the step of applying on keratin fibers the composition as defined in any of the preceding claims for a time sufficient to obtain the desired color.
PCT/EP2006/069932 2005-12-22 2006-12-19 Composition for dyeing keratin fibres with a tetraazapentamethine cationic direct dye, an oxidation base and a particular coupler Ceased WO2007071686A1 (en)

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Publication number Priority date Publication date Assignee Title
WO2009090125A1 (en) 2008-01-17 2009-07-23 Basf Se Polymeric hair dyes
WO2011006946A2 (en) 2009-07-15 2011-01-20 Basf Se Polymeric hair dyes

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EP0004368A2 (en) * 1978-03-23 1979-10-03 Henkel Kommanditgesellschaft auf Aktien Hair dyeing compositions
FR2746306A1 (en) * 1996-03-22 1997-09-26 Oreal DYE COMPOSITIONS OF KERATIN FIBERS CONTAINING PYRAZOLO-AZOLES; THEIR USE FOR DYEING AS COUPLERS, DYEING PROCESS
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EP0004368A2 (en) * 1978-03-23 1979-10-03 Henkel Kommanditgesellschaft auf Aktien Hair dyeing compositions
FR2746306A1 (en) * 1996-03-22 1997-09-26 Oreal DYE COMPOSITIONS OF KERATIN FIBERS CONTAINING PYRAZOLO-AZOLES; THEIR USE FOR DYEING AS COUPLERS, DYEING PROCESS
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009090125A1 (en) 2008-01-17 2009-07-23 Basf Se Polymeric hair dyes
WO2011006946A2 (en) 2009-07-15 2011-01-20 Basf Se Polymeric hair dyes

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