MX2007006460A - Pyrazole azomethines and colorants containing these compounds - Google Patents

Abstract

The object of the present invention is new pyrazole azomethines of Formula (I), (Ia), or (Ib), as well as agents containing these compounds for oxidative coloring of keratin fibers.

Description

PIRAZOL AZOMETINOS AND COLORANTS THAT CONTAIN THESE COMPOUNDS FIELD OF THE INVENTION The present invention relates to novel pyrazole azomethines, as well as to agents containing these compounds to color keratinous fibers, such as hair, silk or wool.

BACKGROUND OF THE INVENTION The process of hair coloring is currently subject to the most varied fashions. Previously, hair coloring was essentially done to cover graying portions, while, currently, there is a growing demand to integrate hair color to current fashion trends, as well as to make it an expression of personality. As in the past, today there are two recognized methods available to color the hair. One method is oxidative hair dyes, with which very permanent coloring results are achieved. The other method is tonalization, which usually has less permanent results. Oxidative hair coloring systems employ developers and coupling agents that produce a broad spectrum of colors. The dye precursors that are documented in various patent texts are essentially benzoic-aromatic or even heteroaromatic compounds, rich in electrons. Because these compounds are sensitive to oxidation as a result of being electron-rich, compounds having alkali groups as acidic adducts are particularly employed. Acid adducts have the advantage that they are highly protected from oxidation by air because of the protonation of amino functions; However, when formulating this type of raw materials as hair dyes, the pH value is usually adjusted to be alkaline by the addition of ammonia or ethanolamine. This causes the formation of salt from the acid adducts; These salts strive cosmetic formulations significantly. The higher salt content may cause phase separation in the worst case; In addition, crystalline deposits can be observed in the fluid formulations due to the higher alcohol content. The result of this is that you can not market various nuances that require active components of color, because of the causes mentioned. In order to prevent oxidative processes in the dye precursors on the one hand, and to protect the cosmetic compositions from a higher salt content on the other, the aim was to provide dye precursors which were adequately protected from oxidation by air and which in turn will not cause any salt loading in the formulations. Moreover, the new dyes should not have any negative effect on the coloring capacity of the formulations. In addition, it aims to allow the production of ionic compounds, which, even as organic salts, hardly exert the formulations. The use of non-ionic azomethines in cosmetic compositions is known from Patent no. DE-OS 35 45 245, wherein the compounds described therein are used as direct penetration dyes. The patent no. WO 99/22707 describes the use of iminophenols to whiten the pigment of the skin. Surprisingly, it was then determined that the protected compounds of the formula (I), in which amino activating groups are derived, are suitably stable with respect to the oxidation by air without exerting any influence on their activity in the peroxide-containing dyes.

DESCRIPTION OF THE INVENTION Therefore, the object of the present application is the pyrazole azomethines of the formula (I), wherein: R1 and R2, independently of one another, represent hydrogen, a dimethylamino group, an aliphatic, aromatic or heteroaromatic group, which, if necessary, are substituted with one or more amino groups, hydroxyl groups, nitrile groups, alkoxy groups , alkylsulfonyl groups, keto groups or groups R1 and R2, together with the carbon atom on which they are based, of heterocyclic, saturated or unsaturated cyclic compounds, wherein R1 or R2 may further contain an ionic group, for example, a group of carboxylic acid, a sulfonic acid group, a quaternary ammonium group, a pyridinium group or an imidazolium group; R3 can be a hydroxyl group, an amino group, a C1-C5 alkylamino group, straight or branched chain, a hydroxyethylamine group, a 2,3-dihydroxy propylamino group, or a benzylamino group, wherein the amino group is preferred; R 4 represents hydrogen, a straight or branched chain C 1 -C 12 alkyl group, a C 2 -C 5 mono- or polyhydroxyalkyl group, straight or branched chain, a C 3 -C 6 alkoxyalkyl group, straight or branched chain, a phenyl group, a benzyl group, which, if necessary, are substituted with one or more C1-C3 alkyl groups, chlorine atoms, bromine atoms, trifluoromethyl groups, C1-C3 alkoxy groups, hydroxyethoxy groups, nitrile groups, hydroxyl groups, or is a five or six membered heteroaromatic group, for example, a pyridine group, a pyrimidine group, a pyridazinyl group, a triazinyl group, a furyl group, a thienyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, which, if necessary, are substituted with one or more C1-C3 alkyl groups, fluorine atoms, chlorine atoms, bromine atoms, trifluoromethyl groups, methoxy groups, methanesulfonyl groups, acid groups carboxylic, carboxylic acid groups co-methyl ester, or carboxylic acid ethyl ester groups, phenyl groups or hydroxymethyl groups, wherein the ringed compounds, for example, quinoline groups, isoquinoline groups or quinoxaline groups, may be considered the heteroaromatic group; and R5 represents hydrogen, a C1-C6 alkyl group, straight or branched chain, a hydroxyalkyl group of C1-C4, an aminoalkyl group of C1-C4, an alkylamino group of C1-C8, a di (C1-C8) group alkylamino, an alkylamino group of C 1 -C 4 alkyl (C 1 -C 4), a di (C 1 -C 4) alkylamino (C 1 -C 4) alkyl group, an aryl group, a heteroaryl group, a carboxylic acid group, a group of carboxylic acid methyl ester, a carboxylic amide group, a nitrile group, wherein hydrogen is preferred; or R3 and R4 have a bridge to each other, such that a compound of the formula (Ia) or (Ib) is formed, wherein: Z1 and Z2, independently of one another, represent a nitrogen atom or a nitrogen atom. carbon substituted with a hydrogen atom, a C1-C5 alkyl group, straight or branched chain, a benzyl residue, a trifluoromethyl group, a hydroxymethyl group, a hydroxyethyl group, a methoxy group, or a phenyl group substituted with a a methyl group, a chlorine atom, a hydroxyl group, a methoxy group or a trifluoromethyl group, and the groups of residues R1, R2 and R5 have the aforementioned meaning. The preferred compounds of the formulas (la) and (Ib) are the compounds in which Z1 and Z2, independently of one another, represent a nitrogen atom, a CH group or a C-CH3 group, where these compounds are especially preferred. of the formulas (la) and (Ib), in which Z1 represents a group C-CH3 and Z2 represents a CH group, or Z2 represents a group C-CH3, and Z1 represents a CH group. Azomethines can be manufactured using usual synthesis methods; an outline of the common synthesis methods can be found in, for example, "Houben-Weyl", Methoden der organischen Chemie [Methods of organic chemistry], Vol. E14b, 222-281, Georg-Thieme-Verlag [editorial], Stuttgart (1990). The azomethines of the present invention are preferably manufactured from pyrazoles with at least one unsubstituted amino group (II) and the aldehydes and / or ketones of the formula (III). In individual cases, it may be advantageous to carry out the synthesis through the condensation reaction of nitroso compounds (IV) with compounds with active methylene (V).

(MI) (IV) (V) Examples of suitable pyrazoles (II) can be, for example: 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-isopropyl pyrazole, 4,5-diamino-1-n-pentyl pyrazole, , 5-diamino-1 - (2-hydroxyethyl) pyrazole, 4,5-diamino-1- (2-methoxyethyl) pyrazole, 4,5-diamino-1-phenyl pyrazole, 4,5-diamino- 1- (4-methylphenyl) pyrazole, 4,5-diamino-1- (4-methoxyphenyl) pyrazole, 4,5-diamino-1- (2-pyridinyl) pyrazole, 4,5-diamino-1- (4- methoxybenzyl) pyrazole, 3 - [(4,5-diamino-1 H -pyrazol-1-yl) methyl] -1-methylpyridinium chloride, 4,5-diamino-1,3-dimethyl-1 H -pyrazole, 4,5-diamino-1 - (2-hydroxyethyl) -3-methyl-1 H-pyrazole, 4,5-diamino-1-methyl-3-phenyl-1 H-pyrazole, 4,5-diamino-1 - (2-hydroxyethyl) -3-phenyl-1 H-pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4 - [(4,5-diamino-1-isopropyl-1 H -pyrazole- 3-ylmethyl) amino] phenol, 2-isopropyl-5-morpholin-4-ylmethyl-2H-pyrazole-3,4-diamine, 2-isopropyl-5-thiophen-2-yl-2H-pyrazole-3,4- diamine, and 4-amino-1,3-dimethyl-5-ethylamino-1 H-pyrazole, as well as acid adducts thereof. The carbonyl (III) components suitable for deriving the pyrazoles (II) of the formula (II) can be, for example, aliphatic, benzoaromatic or heterocyclic aldehydes with five or six members, where the following aromatic aldehydes are preferred: benzaldehyde, anisaldehyde , pyridine-2-carbaldehyde, pyridine-3-carbaldehyde, pyridine-4-carbaldehyde, 2-formyl-1-methylpyridinium methylsulfate, 3-formyl-1-methylpyridinium methylsulfate, 4-formyl-1-methylpyridinium methylsulfate, furan-2 carbaldehyde, thiophen-2-carbaldehyde, vanillin, isovainillin, 4-dimethylamino benzaldehyde, 4-hydroxybenzaldehyde, as well as bifunctional aldehydes, such as phthaldialdehyde, isophthalaldehyde or terephthalaldehyde; the monoaldehydes are especially preferred.

In special cases, aldehyde derivatives can be used in place of free aldehydes, such as their hydrates, aldehyde sulfite, imides, anilines, thioaldehydes, semiacetals or acetals adducts thereof. Mention should be made in particular of the following aldehyde derivatives: 2,2-dimethoxy ethanol and 2,2-dimethoxy ethylamine. Acetals of dimethylformamide leading to imido formamides are also suitable as dimethylformamide derivatives. The following may be mentioned as ketones of the formula (III): acetone, trifluoroacetone, hexafluoroacetone, hydroxyacetone, dihydroxyacetone, 1,3-diamino acetone, dimethylamino acetone, 3-chloro-2-butanone, phenyacylamine, acetoin, cyclopropyl methylketone, cyclohexanone, acetophenone, 2,4-dihydroxyacetophenone, benzalacetone, 3-acetyl indole, 2-acetyl pyrrole, 4-chromanone, 2-indanone, mesityl oxide, trans-4-methoxy-3-butylene-2-one (1-1 -3), 1-methyl-4-piperidone, 2-octadecanone, 3- methylthio-2-butanone, 3-pentene-2-one, phorbol, pseudoionone, α-pyrone, pivaloyl acetonitrile, 2,2,6,6-tetramethyl-4-piperidone and tropolone. The following may be mentioned, for example, as nitroso compounds of the formula (IV): 5-amino-1-methyl-4-nitrosopyrazol, 5-amino-1-isopropyl-4-nitrosopyrazol, 5-amino-4- nitro-1-n-pentyl pyrazole, 5-amino-1- (2-hydroxyethyl) -4-nitroso pyrazole, 5-amino-1- (2-methoxyethyl) -4-nitroso pyrazole, 5-amino-4-nitroso -1-phenyl pyrazole, 5-amino-1- (4-methylphenyl) -4-nitroso pyrazole, 5-amino-1- (4-methoxyphenyl) -4-nitroso pyrazole, 5-amino-4-nitroso-1 - (2-pyridinyl) pyrazole, 5-amino-1- (4-methoxybenzyl) -4-nitroso pyrazole, 5-amino-1,3-dimethyl-4-nitroso-1 H-pyrazole, 5-amino-1 - ( 2-hydroxyethyl) -3-methyl-4-nitroso-1 H-pyrazole, 5-amino-1-methyl-4-nitroso-3-phenyl-1 H-pyrazole, 5-amino-1- (2-hydroxyethyl) -4-Nitroso-3-phenyl-1 H-pyrazole, and 5-amino-3-methyl-4-nitroso-1-phenyl pyrazole. Both the open chain and the cyclic compounds (R 1 linked to R 2) are suitable as ae methylene compounds which constitute a possibility to achieve the nitroso compounds of the formula (IV) wherein, for example, acetylacetone, malodinitrile, can be mentioned, benzoylacetonitrile, cyanoacetic acid ethyl ester, cyanoacetamide, cyclopentane-1,3-dione, cyclohexane-1,3-dione, 1,3-diene-blueberry, Meldrum's acid, barbituric acid, 3-methyl-1-phenyl pyrazolone, and 1-ethyl-1, 2-dihydro-6-hydroxyl-4-methyl-2-oxopyridine-3-carbonitrile as ae methylene compounds. Due to the amount of commercially available aldehydes and ketones, it is possible to adapt the carbonyls components to the amino components, so as to obtain optimum performance in various cosmetic compositions with the resulting azomethines. The following compounds of the formula (I) are particularly preferred: - / V * - [phenylmethylidene] -1 W-pyrazole-4,5-diamine, ^ -. { ^ - (MethyloxyJphenylmethylidene-1-phenyl-1 H-pyrazole ^. S-diarriin, -amino-1 - (1-methylethyl) -1 W-pyrazol-4-yl] imino} methylene) -2- (methyloxy) phenol, 1 - . 1 - [2- (dimethylamino) ethyl] -W * - [(4-methoxyphenyl) methylidene] -1H-pyrazole-4,5-diamamine, - ( { [5-amino-1- (2-hydroxyethyl) -1H-pyrazol-4-yl] methyl} -1-methyl pyridinium methylsulfate, ( { [5-aminono-1 - (4-methoxyphenyl) -1W-pyrazol-4-yl] imino.} Methyl) -2-methoxy-phenol, 1 - (2- pyridinyl) - V * - [3-pyridinylmethylidene] -1H-pyrazole-4,5-diamine, 4- ( { [5-amino-1 - (4-methylbenzyl) -1 W-pyrazol-4-yl] imino} .methyl) phenol, and 3-methyl-N4-. { [4- (methyloxy) phenyl] methylidene} -1-phenyl-1 W-pyrazole-4,5-diamine.

The compounds of the formula (I) according to the present invention sometimes allow a significantly greater color intensity than the corresponding non-derived basic bodies. Therefore, they are very suitable as dye precursors for coloring the keratinous fibers in the oxidative system. Although the compounds of the formula (I) are particularly suitable for use in the coloring of keratinous fibers, for example, wool, silk or hair (particularly, human hair), in principle, it is also possible to color other synthetic or natural fibers, for example, cotton or nylon 66, by using these compounds. To apply in oxidative hair dyes, it is advantageous that the azomethines have no color or only have a slight intrinsic color. Therefore, the applicability of the indoanilines, the indophenols and the indamines is limited by their intrinsic color, and they are generally not considered part of the preferred compounds. A further object of the present invention is an agent for the oxidative coloring of keratinous fibers, for example, wool, skin, feathers or hair, particularly human hair, which contains at least one compound of the formula general (I). The azomethines of the formula (I) are present in the dye of the present invention in an amount of about 0.005 to 20 weight percent, wherein an amount of about 0.01 to 10 weight percent, and particularly 0.1 to 10 weight percent, is preferred. 8 percent by weight. The compounds of the formula (I) can be used alone or in combination with developer substances and / or known coupling agent substances, generally used in oxidative coloring systems. The following may be mentioned in particular as coupling agent substances: N- (3-dimethylaminophenyl) urea, 2,6-diaminopyridine, 2-amino-4 - [(2-hydroxyethyl) amino] anisole, 2,4-diamino-1 -fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1 - (2-hydroxyethoxy) -5 -methylbenzene, 2,4-di [(2-hydroxyethyl) amino] -1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2- (methylamino) pyridine, 2, 6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1- (2-hydroxyethoxy) benzene, 2,4-diamino-1 - (3-hydroxypropoxy) benzene, 2,4-diamino-1- (3-methoxypropoxy) benzene, 1- (2-aminoethoxy) -2,4-diaminobenzene, 2-amino-1- (2-hydroxyethoxy) -4 -methylaminobenzene, 2,4-diaminophenoxy acetic acid, 3- [di- (2-hydroxyethyl) amino] aniline, 4-amino-2-di - [(2-hydroxyethyl) amino] -1-ethoxybenzene, 5-methyl- 2- (1-methylethyl) phenol, 3 - [(2-hydroxyethyl) amino] aniline, 3 - [(2-aminoethyl) amino] aniline, 1,3-di- (2,4-diamino) nofenoxi) propane, di- (2,4-diaminophenoxy) methane, 1,3-diamino-2,4-dimethoxybenzene, 2,6-bis- (2-hydroxyethyl) aminotoluene, 4-hydroxyindole, 3-dimethylaminophenol, 3- diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3- amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2 - [(3-hydroxyphenyl) amino] acetamide, 5 - [(2-hydroxyethyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] phenol, 3 - [(2-methoxyethyl) amino] phenol, 5-amino-2-ethylphenol , 2- (4-amino-2-hydroxyphenoxy) ethanol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol, 3 - [(2,3-dihydroxypropyl) amino] -2-methylphenol, 3 - [( 2-hydroxyethyl) amino] -2-methylphenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3 -dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthyl acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene eno, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 1,3-dihydroxy-2,4- dimethylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5 - [(2-hydroxyethyl) amino] -1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxybenzene, acid 3, 4-diaminobenzoic, 3. 4- dihydro-6-hydroxy-1,4 (2H) -benzoxazine, 6-amino-3,4-dihydro-1,4 (2H) -benzoxacin, 3-methyl-1-phenyl-5-pyrazolone, 5, 6-dihydroxyindole, 5,6-dihydroxyindoline, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, and 2,3-indoline dione, or salts thereof. In order to achieve a very natural tonalization, as well as a fashionable reddish tint, it is advantageous to use compounds of the formula (I) in combination with additional developer substances. The p-phenylenediamines, the p-aminophenols and the 4,5-diaminopyrazoles or salts thereof are possible revealing substances. Mention should be made in particular of the following developer substances: 1,4-diaminobenzene (p-phenylenediamine), 1,4-diamino-2-methylbenzene (p-toluenediamine sulfate), 1,4-diamino-2,6-dimethylbenzene, 1, 4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-dimethylbenzene, 4-phenylaminoaniline, 4-dimethylaminoaniline, 4-diethylaminoaniline, 4- [di (2-hydroxyethyl) amino] aniline, 4 - [(2-methoxyethyl) amino] aniline, 4 - [(3-hydroxypropyl) amino] aniline, 1,4-diamino-2- (2-hydroxyethyl) benzene, 1, 4-diamino-2- (1-hydroxyethyl) benzene, 1,4-diamino-2- (1-methylethyl) benzene, 1,3-bis [(4-aminophenyl) - (2-hydroxyethyl) amino] -2- propanol, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4-aminophenol, 4-amino-3-methylphenol, 4-methylaminophenol, 4-amino-2- (aminomethyl) phenol, 4- amino-2 - [(2-hydroxyethyl) amino] methylphenol, 4-amino-2- (methoxymethyl) phenol, 4-amino-2- (2-hydroxyethyl) phenol, 5-amino-salicylic acid, 2,5-diaminopyridine, 2,4,5,6-tetra-amino-pyrimidine, 2,5,6-triamino-4- (1H) -pyrimidone, 4,5-diamino- 1- (2-hydroxyethyl) -1 H-pyrazole, 4,5-diamino-1- (1-methylethyl) -1 H-pyrazole, 4,5-diamino-1- (4-methylbenzyl) -1 H-pyrazole , 1- (4-chlorobenzyl) -4,5-diamino-1 H-pyrazole, 4,5-diamino-1-methyl-1 H-pyrazole, 4,5-diamino-3-methyl-1-phenyl-1 H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 4,5-diamino-1-pentyl-1 H-pyrazole, 4,5-diamino-1-benzyl-1 H-pyrazole, 4, 5-diamino-1- (4-methoxybenzyl) -1 H-pyrazole, 4,5-diamino-1- (2-hydroxyethyl) -3-methyl-1 H-pyrazole, 2-aminophenol, 2-amino-6- methylphenol and 2-amino-5-methylphenol, or salts thereof. The aforementioned developer substances and coupling agent substances can be used individually or mixed together, so that the known developer substances and coupling agent substances mentioned above are present in the dye of the present invention in a total amount from about 0.01 to 20 weight percent, although from about 0.2 to 8 weight percent is preferred. Moreover, the dye of the present invention can also contain other coloring components, for example, 4- (2,5-diamino benzylamino) aniline or 3- (2,5-diamino benzylamino) aniline, as well as other direct penetration dyes. natural, similar to natural or synthetic synthetics, of the group of anionic (acid) and cationic (alkaline) dyes, triarylmethane dyes, nitro dyes, dispersible dyes and azo dyes, for example, natural dyes, such as indigo or henna, triphenyl dyes methane, such as 4 - [(4'-aminophenyl) - (4'imino-2", 5" -cyclohexadiene-1"-ylidene) methyl] -2-methylaminobenzene monohydrochloride (Cl 42 510) and 4 - [( 4'-amino-3'-methylphenyl) - (4"-imino-3" -methyl-2", 5" cyclohexadiene-1"-ylidene) methyl] -2-methylaminobenzene monohydrochloride (Cl 42 520), dyes aromatic nitro, such as 4- (2'-hydroxyethyl) amino nitrotoluene, 2-amino-4,6-dinitrophenol, 2-amino-5- (2'-hydroxyethyl) amino nitrobenzene, 2-chloro-6- (ethylamino) - 4-nitrophenol, 4-cl Gold-N- (2-hydroxyethyl) -2-nitroaniline, 5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitrophenol, 2-amino-6-chloro-4- nitrophenol, 2-chloro-6- (ethylamino) -4-nitrophenol, and 1 - [(2'-ureidoethyl) amino-4-nitrobenzene, azo dyes, such as 6 - [(4'-aminophenyl) -azo] -5 -hydroxynaphthalene-1-sulphonic acid sodium salt (Cl) 14 805), and dispersible dyes, such as 1,4-diaminoanthraquinone and 1,4,8,8-tetraaminoanthraquinone. The total concentration of direct penetration dyes in the agent of the present invention is from about 0.01 to 10 weight percent, although 0.1 to 5 percent by weight is preferred. The combinations described hereinabove, of the formula (I) of this invention, with oxidative hair dye precursors and / or direct penetration dyes, are applied in a vehicle suitable for color. In addition, the dyes may still contain other conventional additives, for example antioxidants such as ascorbic acid, mercaptoacetic acid or sodium sulfite, as well as essential oils, penetrating agents, buffer systems, complexing agents, preservatives, wetting agents, emulsifiers, thickeners and conditioning agents. The dye formulation according to the present invention can be, for example, a solution, particularly an aqueous or aqueous alcoholic solution, a paste, a cream, a gel, an emulsion or an aerosol preparation. The composition of the solution represents a mixture of the coloring components with the conventional additives for such formulations. It is also possible that the dye of the present invention is in the form of beads, granules or powders that are dissolved in an aqueous preparation, for example, in water or in an aqueous oxidizing agent preparation. Conventional additives in solutions, creams, emulsions, or gels are, for example, solvents such as water, lower aliphatic alcohols, for example, ethanol, propanol or isopropanol, glycerin or glycols, such as 1,2-propylene glycol, and in addition, wetting or emulsifying agents of anionic, cationic, amphoteric or non-ionic classes of surface-active substances, such as fatty alcohol sulfates, oxyethylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkyltrimethylammonium salts, alkylbetaines, oxyethylated fatty alcohols, nonylphenols oxyethylated, fatty acid alkanolamides and oxyacetylated fatty acid esters, and in addition, thickeners, such as higher fatty alcohols, starches, cellulose derivatives, petroleum jelly, paraffin oil and fatty acids, and conditioning agents, such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The aforementioned components are used in conventional amounts for such purposes, for example, wetting agents and emulsifiers in concentrations of about 0.5 to 30 weight percent, thickeners in an amount of about 0.1 to 30 weight percent, and conditioning agents in a concentration of about 0.1 to 5 weight percent. Depending on the composition, the dye of the present invention can be slightly acidic, neutral, or alkaline. In particular, it has a pH value of from 6 to 11.5, wherein the alkaline adjustment preferably takes place using ammonia or organic amines, for example, monoethanolamine and triethanolamine, or amino acids or inorganic bases, such as sodium hydroxide and potassium hydroxide. It is also possible to use combinations of the aforementioned compounds, in particular, a combination of ammonium and monoethanolamine. For pH adjustments in order to make the composition more acidic, the use of organic or inorganic acids can be considered, for example, phosphoric acid, acetic acid, citric acid or tartaric acid. To be used as an oxidative hair dye, the dye described above (pH = 6 to 1.5) is mixed with an oxidizing agent (pH = 2 to 6.5) immediately before use. In this process, the pH value of the hair colorant ready for use is adjusted to a pH value which is determined by the alkaline amount in the vehicle for the color and the amount of acid in the oxidizing agent, as well as by the mix ratio. Depending on the composition, the ready-to-use dyes may react in a slightly acidic, neutral or alkaline manner and have a pH value of about 3 to 1 1, although 5 to 10 are preferable. Hydrogen peroxide or aggregate of compounds of this with urea, melamine, sodium borate or sodium carbonate in the form of an aqueous solution of 3 to 12 percent, preferably 6 percent, as well as oxygen from the atmosphere constitute possibilities for the oxidizing agents to reveal the color of the hair. Based on a 6 percent content of free hydrogen peroxide in the oxidizing agent, the weight ratio between the hair dye and the oxidizing agent is about 5: 1 to 1: 2.; however, 1: 1 is preferred. Essentially larger amounts of oxidizing agents are used when the dye concentrations in the hair coloring agents are higher, or if it is intended to simultaneously achieve greater bleaching of the hair. An amount of this mixture is applied to the hair which is sufficient for the treatment of hair coloring, generally from about 60 g (2.1 oz) to 200 g (7.05 oz), depending on the thickness of the hair, and the mixture is leave in the hair for approximately 10 to 45 minutes, preferably 30 minutes, from 15 ° C (59 ° F) to 50 ° C (122 ° F); Then the hair is rinsed with water and dried. If necessary, then wash the hair with shampoo and rinse again, as necessary, with a light organic acid, such as citric acid or tartaric acid. Then the hair is dried. The dyes of the present invention containing compounds of the formula (I) allow the coloring of the hair with an extraordinary firmness of color, especially with regard to the stability of brightness, color fastness during washing and rub resistance. With respect to the color qualities, the hair colorants according to the present invention provide a wide range of different color tones, particularly in the area of fashionable reddish tones, depending on the type and composition of the colors. color components. The color tones are distinguished by their particular intensity of color and their luminous power. The extremely good color quality of the colorants according to the present application is demonstrated particularly by the fact that these agents also allow a uniform and long-lasting coloration, even in hair previously damaged according to various degrees. The following examples will illustrate the object of the invention without limiting the invention to these examples.

Examples Example 1: Production of 2- (5-amino-4 - ([(4-methylphenyl) methylidene-amino) -1-pyrazole- 1 -Detanol 7.28 g (0.26 oz) (51.2 mmol) of 4.5- are added diamino-1 - (2-hydroxyethyl) pyrazole in 60 mL (2.0 oz) of ethanol at 6.76 g (0.24 oz) (56.3 mmol) of toluyl aldehyde, and stirring at room temperature The solution obtained is initially red, from which is gradually precipitated a yellow product, after 1 hour, suction is applied and the substance is washed with a little cold ethanol.The vacuum drying at 40 ° C (104 ° F) produces 6.4 g (0.2 oz) ( 51% of theory) of pale yellow product 1H-NMR (DMSO-cM: d = 8.47 (s, 1 H), 7.72 (d, 2H), 7.55 (s, 1 H), 7.24 (d, 2H) 5.36 (broad s, 2H), 4.94 (t, 1 H), 3.95 (t, 2H), 3.67 (m, 2H), 2.34 ppm (s, 3H).

Example 2: Production of 2- (5-amino-4- (3-pyridinylmethylidene-1-aminool-1H-pyrazol-1-yl) ethanol The procedure is the same as that of Example 1, but instead of toluylaldehyde, 6.03 g (0.21 g) are used. oz) (56.3 mmol) of pyridine-3-carbaldehyde Yield: 6.6 g (0.2 oz) (56% theory) of yellow product 1 H-NMR (DMSO-ck): d = 8.95 (d, 1 H) 8.55 (m, superimposition of signal, 2H), 8.18 (d, 1 H), 7.59 (s, 1 H), 7.43 (dd, 1 H), 5.59 (s broad, 2H), 4.94 (t, 1 H ), 3.96 (t, 2H), 3.68 ppm (m, 2H).

Example 3: Production of 3 - ((5-amino-1- (2-hydroxyethyl) -1H-pyrazole-4-illimino) methyl) -1-methylpyridinium methylsulfate 2.31 g (0.08 oz) (10 mmol) of the substance are suspended. of Example 2 in 40 mL (1.4 oz) of acetonitrile and added to 1.39 g (0.05 oz) (11 mmol) of dimethyl sulfate; it is stirred for 24 hours at room temperature, where the suspension changes color, from yellow to orange. Then suction is applied, and the substance is washed with a little ethyl acetate. The substance is then dried under vacuum at 40 ° C (104 ° F). This produces 3.2 g (0.1 oz) (89% of theory) of orange solid material. 1 H-NMR (DMSO-ck): d = 9.36 (s, 1 H); 8.84 (d, 1 H); 8.76 (d, 1 H); 8.50 (s, 1 H); 8.12 (m, 1 H); 7.64 (s, 1 H); 5.98 (s, very broad, 2H); 4.37 (s, 3H); 3.97 (t, 2H); 3.69 (t, 2H); 3.38 (s, 3H).

Example 4: Production of 4 - ((r5-amino-1- (4-methylbenzD-1 H-pyrazole-4-illiminolmethylphenol) Dissolve 8.05 g (0.28 oz) (39.8 mmol) of 4,5-diamino-1 - ( 4-methylbenzyl) -1 H-pyrazole in 100 mL (3.38 oz) of 1: 1 (v / v) methanol / water and added to 5 g (0.2 oz) (41 mmol) of 4-hydroxybenzaldehyde. product is precipitated after about 2 minutes.To complete the reaction, the product is further stirred for an additional 20 minutes at room temperature and then sucked in. The product is rinsed with water and dried under vacuum at 40 ° C (104 ° F). Yield: 10.3 g (0.36 oz) (84% theory) of yellow product 1 H-NMR (DMSO-cM: d = 9.79 (broad s, 1 H), 8.40 (s, 1 H), 7.65 ( d, 2H), 7.53 (s, 1 H), 7.12 (d, 2H); 7.07 (d, 2H); 6.81 (d, 2H); 5.44 (broad s, 2H); 5.10 (s, 2H); 2.27 ppm (s, 3H).

Example 5: Production of 3-methyl-N 4 - (4 - (methyloxy) phenylmethylidene) -1-phenyl-1 H-pyrazole-4,5-diamine 4 g (0.1 oz) (15.3 mmol) of 4.5 are dissolved -diamino-3-methyl-1-phenyl pyrazole dihydrochloride and 0.5 g (0.02 oz) of sodium sulfite in 250 mL (8.45 oz) of water, and the pH value is adjusted to 7 by the addition of concentrated ammonia solution . Subsequently 2.21 g (0.08 oz) (16.2 mmol) of 4-methoxybenzaldehyde are added. After a few minutes, the reaction mixture becomes cloudy, and an oily brown-orange precipitate forms. The mixture is diluted with 40 mL (1.4 oz) of isopropanol and stirred further; only the oily deposit solidifies. After 2 hours of agitation, suction is applied, and the mixture is washed thoroughly with water. Vacuum drying at 40 ° C (104 ° F) produces 2.4 g (0.08 oz) (51% theory) of yellowish solid material. 1 H-NMR (DMSO-ck): d = 8.55 (s, 1 H); 7.86 (d, 2H); 7.62 (m, 2H); 7.50 (m, 2H); 7.33 (m, 1 H); 7.01 (d, 2H); 5.48 (broad s, 2H); 3.82 (s, 3H); 2.34 ppm (s, 3H).

Example 6: Production of N4- (r4- (methyloxy) phenyl-1-methylidene) -1-pentyl-1 H-pyrazole-4, 5-diamine Dissolve 4 g (0.1 oz) (16.6 mmol) of 4,5-diamino-1-pentyl pyrazole dihydrochloride and 0.5 g (0.02 oz) of sodium sulfite in 100 mL (3.38 oz) of water, and it is neutralized by the addition of concentrated ammonia solution. 2.4 g (0.08 oz) (17.6 mmol) of anisaldehyde in 40 mL (1.4 oz) of isopropanol are added to this solution with the application of vigorous stirring. After a few minutes, the solution becomes cloudy, and a yellowish precipitate forms. After 2 hours, suction is applied, and the solution is washed thoroughly with water. Vacuum drying at 40 ° C (104 ° F) produces 3.8 g (0.1 oz) (80% theory) of yellow product. 1 H-NMR (DMSO-cM: d = 8.43 (s, 1 H); 7.76 (d, 2H); 7.50 (s, 1 H); 6.99 (d, 2H); 5.38 (s, broad, 2H); 3.85 (m, superimposition of signal, 5H); 1.66 (m, 2H); 1.27 (m, 4H); 0.86 ppm (t, 3H).

Example 7: Production of 4 - (([5-amino-1- (1-methyl-ethyl) -1 H -pyrazol-4-illiminolmethyl) -2- (methyloxy) phenol 4.76 g (0.18 oz) (20 mmol) are dissolved of 4,5-diamino isopropyl pyrazole sulfate and 0.5 g (0.02 oz) of sodium sulfite in 200 mL (6.76 oz) of water, and the pH value is adjusted to 7 by the addition of concentrated ammonia solution. 3.35 g (0.12 oz) (22 mmol) of vanillin are added, after a few minutes, the reaction mixture becomes cloudy and light yellow crystals are formed, After 2 hours of stirring, suction is applied, and the mixture is washed with water. bottom with water Vacuum drying at 40 ° C (104 ° F) produces 4.27 g (0.15 oz) (78% theory) of yellow solid material 1 H-NMR (DMSO-ck): d = 9.36 (s) , broad, 1 H), 8.37 (s, 1 H), 7.50 (m, superimposition of signal, 2H), 7.15 (dd, 1 H), 6.80 (d, 1 H), 5.32 (s, broad, 2H); 4.44 (septet, 1 H); 3.84 (s, 3H); 1.30 ppm (d, 6H).

Example 8: color example 0. 30 g (0.01 oz) Ascorbic acid 0.40 g Sodium sulfite 10.00 g (0.35 oz) Sodium lauryl ether sulfate, 28% aqueous solution 7.85 g (0.28 oz) Ethanol 12.5 mmol Compound of the formula (I) according to the Table 1 12.5 mmol Coupling substance according to Table 1 9.10 g (0.32 oz) Ammonia, 25% aqueous solution csp 100.00 g Water, demineralized Immediately before use, 100 grams (3.53 oz) of the aforementioned vehicle for the color is mixed with 100 grams (3.53 oz) of an aqueous 6% hydrogen peroxide solution, and the ready-to-use dye solution obtained is applied to the hair bleached in the necessary amount. After an action period of 30 minutes at 40 ° C (104 ° F), the hair is shampooed, rinsed with water and dried. The color tones obtained and the values L * a * b * are compiled in Table 1. The color measurements L * a * b * indicated in the present application were obtained using a color measuring device Chromameter II, manufactured by Minolta. The value L * represents clarity (the smaller the value L *, the greater the intensity of the color), and the value a * is a measure of the reddish portion (the greater the value a *, the greater the reddish portion ). The b * value is a measurement of the blue portion of the color, where the blue portion increases as the b * value becomes more negative.

Table 1: color results of various combination of developer / coupling agent 10 15 Example 9: dye for the creamy, alkaline oxidative hair . 00 g cetyl-stearyl alcohol (50/50) 5.00 g (0.18 oz) glycerin monostearate 2.00 g (0.07 oz) Cocamide DEA 10.00 g (0.35 oz) sodium lauryl ether sulfate, 28% aqueous solution 0.30 g ascorbic acid 0.40 g sodium sulfite 0.61 g (0.02 oz) dye according to Example 1 0.32 g 1,4-diamino-2-methoxymethyl benzene sulfate 0.16 g (0.005 oz) 4-amino-3-methylphenol 0.50 g (0.02 oz) 3- . { [phenylmethylidene] amino} phenol (CAS [18277-39-9]) 0.13 g (0.005 oz) Resorcinol 0.17 g (0.006 oz) 2,4-dimethyl resorcinol 0.22 g (0.008 oz) 2-amino-6-chloro-4-nitrophenol hydrochloride 4.50 g (0.18 oz) ammonia, 25% aqueous solution csp 100.00 g water, demineralized Immediately before use, mix 100 grams (3.53 oz) of the vehicle for the above-mentioned color (pH = 10.2) with 100 grams (3.53 oz) of a 6% aqueous solution of hydrogen peroxide, and the dye solution is ready to use obtained it is applied to the hair types mentioned below in the necessary quantity. After an action period of 30 minutes at 40 ° C (104 ° F), the hair is washed with a neutral shampoo, rinsed with water and dried. The color results obtained with the various hair types are compiled in Table 2. Table 2: Example 10: oxidative hair dye, neutral 4. 00 g (0.14 oz) Plantaren 2000 UP / NP 0.20 g (0.007 oz) Disodium EDTA 5.00 g (0.18 oz) ethanol 0.34 g compound according to Example 7 0.17 g (0.006 oz) 6-hydroxindole csp 100.00 g ( 3.53 oz) water, demineralized Immediately before use, mix 100 grams (3.53 oz) of the vehicle for the above-mentioned color (pH = 7.2) with 100 grams (3.53 oz) of a 6% aqueous solution of hydrogen peroxide, and the coloring solution is ready to use obtained it is applied to the bleached hair in the necessary amount. After an action period of 30 minutes at 40 ° C (104 ° F), the hair is washed with a neutral shampoo, rinsed with water and dried. The hair has a cognac coloring tone. Unless indicated otherwise, all percentages expressed in the present application represent percentages by weight.

Claims (9)

1. The pyrazole azomethines of the formula (I) characterized in that R1 and R2, independently of one another, represent hydrogen, a dimethylamino group, an aliphatic, aromatic or heteroaromatic group, which, if necessary, are substituted with one or more amino groups, hydroxyl groups, nitrile groups, alkoxy groups, alkylsulfonyl groups or keto groups, or groups R1 and R2, together with the carbon atom on which they are based, of heterocyclic, saturated or unsaturated cyclic compounds, wherein R1 or R2 may also contain an ionic group; R3 may be a hydroxyl group, an amino group, a C1-C5 alkylamino group, straight or branched chain, a hydroxyethylamino group, a 2,3-dihydroxy propylamino group, or a benzylamino group; R4 represents hydrogen, a C1-C12 alkyl group, straight or branched chain, a C2-C5 mono- or polyhydroxyalkyl group, straight or branched chain, a C3-C6 alkoxyalkyl group, straight or branched chain, a phenyl group, a benzyl group, which, if necessary, are substituted with one or more C1-C3 alkyl groups, chlorine atoms, bromine atoms, trifluoromethyl groups, C1-C3 alkoxy groups, hydroxyethoxy groups, nitrile groups, hydroxyl groups, or is a five or six membered heteroaromatic group; and R5 represents hydrogen, a C1-C6 alkyl group, straight or branched chain, a hydroxyalkyl group of C1-C4, an aminoalkyl group of C1-C4, an alkylamino group of C1-C8, a di (C1-C8) group alkylamino, an alkylamino group of C 1 -C 4 alkyl (C 1 -C 4), a di (C 1 -C 4) alkylamino (C 1 -C 4) alkyl group, an aryl group, a heteroaryl group, a carboxylic acid group, a group of carboxylic acid methyl ester, a carboxylic amide group or a nitrile group; or R3 and R4 have a bridge to each other, such that a compound of the formula (la) or (Ib) is formed, wherein Z1 and Z2, independently of one another, represent a nitrogen atom or a carbon atom substituted with a hydrogen atom, a C1-C5 alkyl group, straight or branched chain, a benzyl residue, a trifluoromethyl group , a hydroxymethyl group, a hydroxyethyl group, a methoxy group, or a phenyl group substituted with a methyl group, a chlorine atom, a hydroxyl group, a methoxy group or a trifluoromethyl group, and the residue groups R1, R2 and R5 they have the meaning mentioned above.

2. The pyrazole azomethine according to claim 1, characterized in that it is selected from the group comprising 1-methyl-W * - [phenylmethylidene] -1-pyrazole-4,5-diamine, / \ -. { [4- (methyloxy) phenyl] methylidene} -1-pentyl-1 H-pyrazole-4,5-diamine, 4- ( { [5-amino-1- (1-methylethyl) -1 H -pyrazol-4-yl] imino} methyl) -2- (methyloxy) phenol, 1- [2- (dimethylamino) ethyl] -A ^ - [(4-methoxyphenyl) methylidene] -1W-pyrazole-4,5-diamine, 3- ( { [5amino -1 - (2-hydroxyethyl) -1 H -pyrazol-4-yl] imino.} Methyl) -1-methyl pyridinium methylsulfate, 4- ( { [5-amino-1- (4-methoxyphenyl) - 1 H-pyrazol-4-yl] imino.} Methyl) -2-methoxyphenol, 1- (2-pyridinyl) -A / * - [3-pyridinyl methylidene] -1W-pyrazole-4,5-diamine, 4- ( { [5-amino-1- (4-methylbenzyl) -1H-pyrazol-4-yl] imino} methyl) phenol, and 3-methyl-N4-. { [4- (methyloxy) phenyl] methylidene} -1-phenyl-1 H-pyrazole-4,5-diamine, or mixtures of these compounds. An agent for the oxidative coloring of keratinous fibers, characterized in that it contains at least one pyrazole azomethine according to claims 1 or 2. 4. The agent according to claims 1 to 3, further characterized in that the compound of Formula (I) is present in a total amount of 0.005 to 20 weight percent. The agent according to claims 1 to 4, further characterized in that the agent also contains at least one coupling agent substance and / or developer substance. The agent according to claims 1 to 5, further characterized in that the agent also contains at least one natural, synthetic or natural direct penetration dye. The agent according to one of claims 1 to 6, further characterized in that the agent has a pH value of 6 to 11.5. The agent according to claims 1 to 7, further characterized in that the agent is mixed with an oxidizing agent before use. The agent according to any one of claims 1 to 8, further characterized in that it is a hair colorant.