WO2005117817A1

WO2005117817A1 - M-phenylene diamine coupler components

Info

Publication number: WO2005117817A1
Application number: PCT/EP2005/004701
Authority: WO
Inventors: Georg KNÜBEL; Horst Höffkes; Ralf Nemitz
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2004-05-28
Filing date: 2005-04-30
Publication date: 2005-12-15
Also published as: EP1748755A1; DE102004026732A1

Abstract

The invention relates to an agent for dying keratin fibers, particularly human hair, containing, in a cosmetically acceptable carrier and in the form of coupler components, at least one m-phenylene diamine derivative of general formula (I) or salts thereof, in which: R1, R2, R3, R4, independent of one another, represent H, C1-6-alkyl, C2-6-hydroxyalkyl, C2-6-alkoxyalkyl, C2-6-aminoalkyl, C3-10-alkylaminoalkyl, C4-12-dialkylaminoalkyl, with the provision that at least one of the radicals R1, R2, R3, R4 is not H, and; R5 and R6, independent of one another, represent H, C1-6-hydroxyalkyl and C2-6-alkoxyalkyl, whereby also one of the radicals R5, R6 can represent -OH, C1-6-alkoxy, -NH2, -NHR, -NR2 with R being, independent of one another, optionally OH-substituted C1-4-alkyl.

Description

m-phenylenediamine intermediates

The present invention relates to agents for dyeing keratin fibers which contain special m-phenylenediamine derivatives, a process for dyeing hair with these agents, and to these m-phenylenediamine derivatives themselves and intermediates which are formed in the preparation of these compounds.

For the coloring of keratin fibers, especially human hair, the so-called oxidation coloring agents play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and

Intermediates. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.

Primary aromatic amines with a further free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and their derivatives are usually used as developer components ,

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5, 6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5- Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol ₅ 2-aminomethyl-4-aminophenol, 2 -Hydroxy-4,5,6-triarninopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2- hydroxyethyl) -N, N'-bis (4-aminophenyl) diamino-propan-2-ol.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. 1-Naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resor- cinmonomethyl ether, m-phenylenediamine, l-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

4-alkyl and 2-alkyl-substituted 1,3-phenylenediamines have long been known as coupling components in oxidative hair colors. For example, 2,4-diaminotoluene has been used for many years in the past, for example, as a blue coupler for p-phenylenediamine and p-toluenediamine. In such systems, substituted systems have also been developed on the N atoms and the methyl group of these basic structures.

Good oxidation dye precursors should form the desired color shades in sufficient intensity and fastness in the oxidative coupling. They should also have a good ability to draw onto the fiber, with no noticeable differences between stressed and freshly regrown hair, in particular with human hair (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids. After all, if they are used as hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloring achieved should be easily removed from the hair again by bleaching, if it does not correspond to the individual wishes of the individual and is to be reversed.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye components which show the above property profile and which are also unproblematic in toxicological and dermatological terms.

The object of the present invention was therefore to develop new coupler components which also meet the requirements placed on oxidation dye precursors in terms of toxicological and dermatological properties, and enable dyeing in a wide range of colors with good fastness properties.

It has been found according to the invention that special m-phenylenediamine derivatives meet the requirements imposed on coupler components to a high degree. The coupler components according to the invention make it possible, in particular, to produce intense red tones with good application properties.

The invention therefore firstly relates to agents for dyeing keratin fibers, in particular human hair, containing at least one m-phenylenediamine derivative of the general formula (I) as a coupler component in a cosmetically acceptable carrier.

(0 with the meaning

R ', R ² , R ³ R ⁴ independently of one another H, -C _-0 -alkyl, C ₂ . ₆ -hydroxyalkyl, C ₂ . ₆ alkoxyalkyl, C _2-6 aminoalkyl, C ^ o-alkylaminoalkyl, dialkylaminoalkyl C _{4- 12,} with the proviso that at least one of the radicals R ^1, R ^2, R ^3, R ⁴ is different from H,

R ⁵ , R ⁶ independently of one another H, C _1-6 alkyl, -C. ₆ -hydroxyalkyl, C ₂ . ₆ -alkoxyalkyl, where one of the radicals R ⁵ , R ⁶ -OH, C _1-6 -alkoxy, - NH2, -NHR, -NR ₂ with R in each case independently of one another may optionally also be OH-substituted C _-4 alkyl, or salts thereof.

Keratinic fibers are to be understood according to the invention to mean furs, wool, feathers and in particular human hair. Although the oxidation colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent them from being used in other areas, particularly in color photography.

Since the m-phenylenediamine derivatives according to the invention are amino compounds, the known acid addition salts can be prepared from them in the usual way. The invention therefore relates both to the compounds present in free form and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.

Examples of the C ₁ -C ₆ -alkyl groups, preferably C ₁ -C 4 -alkyl groups mentioned as substituents in the compounds according to the invention, which may be linear or branched, are the groups methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl , Ethyl and methyl are preferred alkyl groups. A 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group can be mentioned as preferred C ₂ - to C ₆ - (mono) hydroxyalkyl group. A 2-hydroxyethyl group is particularly preferred. C _-6- Alkoxyalklyreste have a total of 2 to 6 carbon atoms, which are distributed over the alkoxy and the alkyl radical. Up to 5 carbon atoms can thus be present in the alkoxy or alk l radical. It is preferably a C _1-3 alkoxy-C _1-3 alkyl radical, particularly preferably C 1. ₂ -alkoxy-Cι- ₂ alkyl radical. Both the alkoxy and the alkyl radical can be linear or branched. They are preferably linear. C _2-6 aminoalkyl residues, preferably C _2-4 aminoalkyl residues, C3. ₁₀ -alkylaminoalkyl radicals, preferably C _2-6 -alkylaminoalkyl radicals and C _4- ι ₂ -dialkylaminoalkyl radicals, preferably C ₃ . ₉ -Dialkylaminoalkyl radicals can each have linear or branched alkyl radicals. Each individual alkyl group preferably has 1 to 3 carbon atoms. The alkyl radicals present in the respective groups are preferably defined as above for the pure alkyl radicals. An m-phenylenediamine derivative of the general formula (I) particularly preferably has a maximum of four OH groups, preferably a maximum of two OH groups. The m-phenylenediamine derivative of the general formula (I) preferably contains a maximum of four nitrogen atoms, particularly preferably two nitrogen atoms. In total, apart from the hydroxyl groups, there are a maximum of four further oxygen atoms in the m-phenylenediamine derivative of the general formula (I), preferably a maximum of a further two oxygen atoms, in particular no further oxygen atoms.

Preferred meanings of the radicals are listed below.

According to a preferred embodiment, R ¹ , R ² , R ³ , R ^{4 are} independently hydrogen, Cj _-4 -alkyl or C _2-4 -HydiOxyalkyl. R ¹ and R ^{3 are} particularly preferably hydrogen and R ² and R ^{4 are} hydrogen or C _2-4 -hydroxyalkyl.

R ¹ and R ^{3 are} particularly preferably hydrogen and R ² and R ^{4 are} -CH ₂ CH ₂ OH.

According to one embodiment of the invention, R ⁵ and R ⁶ independently of one another are hydrogen, C _-4 alkyl or C _-4 hydroxyalkyl.

R ^{5 is} particularly preferably hydrogen and R is methyl.

According to a further particularly preferred embodiment of the invention, R ¹ , R ³ , R ⁵ , R ^{6 are} hydrogen and R ² , R ⁴ -CH ₂ -CH ₂ OH.

The agent according to the invention can contain one or more, for example at least two different m-phenylenediamine derivatives of the general formula (I).

The m-phenylenediamine derivatives of the formula (I) can be prepared using conventional organic methods. As an example, reference is made to the experimental procedures in the context of the exemplary embodiments. The agents for dyeing keratin fibers according to the invention preferably contain the at least one m-phenylenediamine derivative of the general formula (I) in an amount of 0.001 to 15% by weight, particularly preferably 0.05 to 5% by weight, based on the finished agent ,

The agent for dyeing keratin fibers can be selected from any suitable agents which are particularly suitable for dyeing human hair. In particular, an otherwise customary carrier of agents for coloring human hair is used as the cosmetically acceptable carrier. The colorants according to the invention can, apart from the m-phenylenediamine derivatives of the general formula (I), be composed of known colorants or contain the usual ingredients for them. Examples of other suitable ingredients preferred according to the invention are given below.

Agents according to the invention can have the following ingredients in the amounts indicated.

Developer 0.05 - 5%

Coupler 0.05 - 5%

Surfactants, emulsifiers 0.1 - 20%

Fatty alcohols and others

Emulsifier 0.5 - 20%

Complexing agent 0.05 - 10%

Buffer agent 0.1 - 1.0%

Solubilizer +

Solvent 0.5 - 15% pH adjusting agent as required

Perfume oils 0.1 - 0.6%

Polymers 0.1 - 5% Water 50 - 98%

Suitable colorant compositions are described, for example, in DE-U 1-299 11 819, DE-A-101 25 451, DE-Ul-201 11 036, Cosmetics, ed. W. Umbach, 2nd ed. 1995, G. Thieme Verlag Stuttgart, New York.

In addition to the m-phenylenediamine derivatives of the formula (I), the colorants according to the invention can also contain at least one developer component.

Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5, 6-tetraaminopyrimidine and the like are usually used as developer components Derivatives used.

It may be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

where G ¹ represents a hydrogen atom, a d- to C ₄ - alkyl radical, a C _\ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C \ - to C) - alkoxy- (Cι - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C 1 -C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G ² represents a hydrogen atom, a C 1 -C ₄ -alkyl radical, a - C ₄ - monohydroxyalkyl radical, a C ₂ - C ₄ polyhydroxyalkyl radical, a (C 1 -C ₄ ) - Alkoxy- (Cι- to C ₄ ) alkyl radical or a C _\ - to C ₄ - alkyl radical which is substituted with a nitrogen-containing group; G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C \ - to C ₄ - alkyl group, a Ci to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl group, a Ci to C ₄ - hydroxyalkoxy radical, a Ci to C ₄ -Acetylaminoalkoxyrest, a C _\ - to C ₄ - Mesylaminoalkoxyrest or d- to C ₄ -Carbamoylaminoalkoxyrest; G represents a hydrogen atom, a halogen atom or a C 1 -C ₄ -alkyl radical or if G ³ and G ^{4 are in the} ortho position to one another, they can together form a bridging α, co-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the C 1 -C ₄ -alkyl radicals mentioned as substituents in the compounds are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Preferred C to C ₄ alkoxy radicals are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ -C ₄ -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C - to C ₄ - polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are F, CI or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of formula (El) are especially the amino groups, monoalkylamino groups CJ to C, C _\ - to C ₄ dialkylamino, CJ to C ₄ - trialkylammonium, CJ to C ₄ -Monohydroxyalkylammogruppen, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N _^ dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) aniline, N, N-bis (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (ß-hydroxyethyl) -amino- 2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) -amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (ß-hydroxypropyl) -p-phenylenediamine, 2-

Hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-

Hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (lH -imidazol- l-yI) propyl] amine, where in place of 3-methylphenyl generally phenyl or Cι _-6 - alkylphenyl and 5,8-diaminobenzo-l, 4-dioxane, and their physiologically tolerable salts.

P-Phenylenediamine derivatives of the formula (E1) which are very particularly preferably used according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, N- (4-Amino-3-methylphenyl) -N- [3- (1H-imidazol-l-yl) propyl] amine, where phenyl or C _1-6 -alkylphenyl can also generally be present instead of 3-methylphenyl and N, N -Bis- (ß-hydroxyethyl) -p-phenylenediamine.

It can also be preferred according to the invention to use, as developer component, compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

where: Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical, which is optionally substituted by a Cp to C ₄ alkyl radical, by a Cj to C - hydroxyalkyl radical and / or by a bridge Y or the is optionally part of a bridging ring system, the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as, for example, a linear or branched alkylene chain or an alkylene ring, which is composed of one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen or sulfur - Or nitrogen atoms can be interrupted or terminated and possibly substituted by one or more hydroxyl or Cj to C ₈ alkoxy radicals, or a direct one. Binding, G ⁵ and G ⁶ independently represent a hydrogen or halogen atom, a Cj to C ₄ alkyl radical, a Cp to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Ci to C ₄ Aminoalkyl radical or a direct connection to the bridge Y, G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C 1 -C ₄ -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridge Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom. The substituents used in formula (E2) are defined analogously to the above statements.

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methyl-aminophenyl) tetramethylene diamine, N, N'-diethyl-N, N ' -bis- (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol , N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p -phenylenediamine and l, 10-bis- (2 ', 5'-diaminophenyl) - 1,4,7,10-tetraoxadecane and their physiologically tolerable salts.

Very particularly preferred dinuclear developer components of the formula (E2) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis (2 ', 5'-diaminophenyl) - 1, 4,7, 10-tetraoxadecane or one of their physiologically tolerable salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

where: G ¹³ represents a hydrogen atom, a halogen atom, a C 1 -C ₄ -alkyl radical, a C 1 -C ₄ monohydroxyalkyl radical _5, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C 1 -C ₄ ) alkoxy - (C 1 -C ₄ ) -alkyl radical, a C 1 -C ₄ -aminoalkyl radical, a hydroxy- (C] - to C ₄ ) -alkylamino radical, a C 1 -C ₄ -hydroxyalkoxy radical, a C 1 -C ₄ -hydroxyalkyl- (Crbis C ₄ ) -aminoalkyl radical or a (di-Cp to C ₄ -alkylamino) - (C! - C) -alkyl radical, and G ¹⁴ represents a hydrogen or halogen atom, a C to C ₄ alkyl group, a d to C ₄ monohydroxyalkyl group, a C ₂ to C polyhydroxyalkyl group, a (Ci to C ₄ ) alkoxy (C 1 to C ₄ ) alkyl group, a Cj to C ₄ aminoalkyl or a Ci to C ₄ cyanoalkyl group, G ¹⁵ represents hydrogen, a C to C ₄ alkyl group, a Cr to C ₄ monohydroxyalkyl group, a C to C ₄ polyhydroxyalkyl group, a phenyl group or one Benzyl radical, and G ¹⁶ represents hydrogen or a halogen atom.

The substituents used in formula (E3) are defined analogously to the above statements.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (ß-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, ß-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically tolerable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino- 2- (diethylaminomethyl) -phenol.

The developer component can also be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts. Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) -amino-3-ammo-pyridine , 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4.5 -Diamino-l-methylpyrazole, 4,5-diamino-1 - (ß-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4-chlorobenzyl) -pyrazole, 4,5-diamino -l, 3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3-phenylpyrazole, 4-amino-l, 3-dimethyl-5-hydrazinopyrazole, l -Benzyl-4,5-diamino ~ 3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole, 4,5-diamino-l-tert.-butyl-3-methylpyrazole, 4,5 -Diamino- 1 - (ß-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-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-l-isopropylpyrazole, 4-amino-5- (ß-aminoethyl) - amino-l, 3-dimethylp yrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (ß-hydroxyethyl) - amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:

where: G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C 1 -C ₄ -alkyl radical, an aryl radical, a Cr to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkyl radical a (Cr to C ₄ ) alkoxy- (C] - to C ₄ ) - alkyl radical, a Cj to C ₄ - aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a ( Cr to C ₄ ) -alkylamino- (Cr to C ₄ ) -alkyl radical, a di - [(Cr to C ₄ ) -alkyl] - (Cr to C ₄ ) -aminoalkyl radical, the dialkyl radicals optionally having a carbon cycle or a Form a heterocycle with 5 or 6 chain links, a Cr to C ₄ - hydroxyalkyl or a di (Cj to C ₄ ) - [hydroxyalkyl] - (Cr to C ₄ ) - aminoalkyl radical, the X radicals independently represent one another Hydrogen atom, a Cr to C ₄ alkyl radical, an aryl radical, a Cj to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cr to C ₄ aminoalkyl radical, a (Cr to C ₄ ) Alkylamino- (Cr to C ₄ ) -alkyl radical, a di - [(Cr to C ₄ ) alkyl] - (Cr to C ₄ ) - aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links , a Cr to C ₄ hydroxyalkyl or a di (Cr to C ₄ hydroxyalkyl) aminoalkyl radical, an amino radical, a Cj to C ₄ alkyl or di (Cr to C ₄ hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0 if p + q is equal to 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ^I9 G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7); if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

The substituents used in formula (E4) are defined analogously to the above statements.

If the pyrazole- [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can mention in particular: pyrazole- [1,5-a] pyrimidine-3,7-diamine; 2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine; Pyrazole [l, 5-a] pyrimidine-3,5-diamine; 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine; 3 - aminopyrazole- [1,5-a] pyrimidin-7-ol; 3-aminopyrazole [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-aminopyrazole [l, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 2 - [(7-aminopyrazole [l, 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 5,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine; 3-Amino-7-dimethylamino-2,5-dimethylpyrazole [l, 5-a] pyrimidine; as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

The pyrazole [1,5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

In a further preferred embodiment, the colorants according to the invention contain at least one further coupler component.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Suitable coupler substances are, in particular, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, l-phenyl -3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 -Chlor-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Further coupler components preferred according to the invention are - m-aminophenol. and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-diethyl-3- aminophenol, 3-trifluoroacetyIamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2 - methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol , - o-aminophenol and its derivatives, - m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1, 3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2- amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2 ', 4'-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino -3-bis- (2'-hydroxyethyl) aminobenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino-no) ethanol, 3-amino-4- ( 2-methoxyethoxy) -5-methylphenylamine, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-l-methylbenzene, di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2 ~ amino-5-chloro-3-hydroxypyridine, 3-amino -2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyri din, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-l-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-l-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, morpholine derivatives such as 6-hydroxybenzomorpholine and 6-amino benzomorpholine, quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as for example l-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4, 6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

- Methylenedioxybenzene derivatives such as l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene. Further coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and 2 - ({3- [2-hydroxyethyl ) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2- [ (3-morpholin-4-ylphenyl) amino] ethanol.

The following coupler / developer combinations have proven to be particularly suitable according to the invention:

N, N-bis (2-hydroxyethyl) -p-phenylenediamine, p-toluenediamine, 2,4,5, 6-tetraaminopyrimidine, 1 - (2-hydroxyethyl) -2,5-diaminobenzene, 1 - (2nd -Hydroxyethyl) 4,5-diaminopropyl and bis- (2-hydroxy-5-aminophenyl) methane, in each case in combination with the example compounds, in particular 2 - ({3- [2-hydroxyethyl) amino] -5-methylphenyl} amino ) ethanol.

In a further embodiment of the present invention, the colorants can contain at least one precursor of a nature-analog dye. Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Derivatives of 5,6-dihydroxyindoline of the formula (Ha) are particularly suitable as precursors of nature-analogous hair dyes,

in which independently of one another - R ¹ stands for hydrogen, a C ¹ -C ₄ -alkyl group or a C ¹ -C ₄ -hydroxy-alkyl group, - R ² stands for hydrogen or a -COOH group, the -COOH group also can be present as a salt with a physiologically compatible cation, - R ³ stands for hydrogen or a dC ₄ -alkyl group, R ⁴ stands for hydrogen, a CrC ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C 1 -C ₄ alkyl group, and R ⁵ represents one of the groups mentioned under R ⁴ , and physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular that 5,6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole of the formula (IIb) are also outstandingly suitable as precursors of naturally analogous hair dyes,

in which independently of one another - R ¹ stands for hydrogen, a CrC ₄ alkyl group or a C 1 -C ₄ hydroxyalkyl group, R ² stands for hydrogen or a -COOH group, the -COOH group also as a salt with a physiologically acceptable cation may be present, - R ³ represents hydrogen or a C 1 -C ₄ alkyl group, - R ⁴ represents hydrogen, a C 1 -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ represents a CrC ₄ alkyl group, and R ⁵ represents one of the groups mentioned under R, and physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 are to be emphasized -Dihydroxyindol.

The indoline and indole derivatives can be in the colorants according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochlorides, sulfates and hydrobromides, are used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In a further embodiment, it can be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-amino acids are arginine, omithin, lysine, serine and histidine, in particular arginine. In addition to the m-phenylenediamine derivatives of the formula (I) according to the invention, in a further preferred embodiment of the present invention, the colorants according to the invention can contain one or more substantive dyes for shading. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and l , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, l, 4-bis (ß-hydroxyethyl) amino-2-nitrobenzene, 3 -nitro-4- (ß-hydroxyethyl) aminophenol, 2 - (2'-Hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1 - (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2 '- carbons acid, 6-nitro-1, 2,3, 4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

The agents according to the invention can also contain a cationic direct dye. Particular preference is given to (a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems which are substituted by a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as (c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, to which at this point explicit reference is made to claims 6 to 11. Preferred cationic direct dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

CI ^"

The compounds of the formulas (DZl), (DZ3) and (DZ5), which are also known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic direct dyes of group (c).

The cationic direct dyes that are sold under the Arianor brand are also very particularly preferred cationic direct dyes according to the invention. The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, the hair colorants according to the invention, due to the production process for the individual dyes, may also contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair dyeing and toning agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials." ", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, Mannheim.

The inventive. Colorants can also contain all active ingredients, additives and auxiliaries known for such preparations. In many cases, the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps ), Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, methyl alpha-sulfofatty acid esters of fatty acids with 12 to 18 carbon atoms , Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ - CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030 , sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 354, sulfonates of unsaturated fatty acids with 12 to 24 C atoms and 1 to 6 double bonds according to DE-A-3926 344, Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated Cg-C ₂₂ carboxylic acids, such as oleic acid, stearic acid, Isostearic acid and palmitic acid.

Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such compounds are, for example, adducts of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group, C ₁₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide. Glycerin, C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well as addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ^! O- (Z) _χ . These connections are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When so-called "oxo alcohols" are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate. The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R ¹ consists essentially of C ₈ - and Cι ₀ alkyl groups, essentially from C ₁ 2- and C ₁₄ - alkyl groups, essentially from C ₈ - to C ^ alkyl groups or essentially consists of C ₁₂ - to C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as the sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used in accordance with the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit. Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ⁽⁾ - or -SO ₃ ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and to form internal ones Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and Cι ι _2- ₈ acyl sarcosine.

According to the invention, cationic surfactants in particular can be those of the quaternary ammonium compound, esterquat and amidoamine type.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chloride and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quatemium-27 and Quatemium-83 known imidazolium compounds. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the brands Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, a N, N-bis (2-Palmitoyloxy- ethyl) dimethyl ammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances that available under the brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine is.

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Coming 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride". The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts when converting fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Furthermore, the colorants according to the invention can contain further active ingredients, auxiliaries and additives, such as, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxane groups , Dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium-methochloride copolymers and quaternized polyvinylalcohol-acrylate-methyl-aminopropyl-acrylate-trimethylammonylammonyl polymers, for example, acrylotomethylammonylammonylammonylammonyl polymers, for example Copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, cross-linked polyacrylic acids, vinyl acetate / crotonic acid cop polymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl-acrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxy methyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active substances that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl l-alkylamidoethyl -2-alkylimidazolinium methosulfate

Defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those from groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, Sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root. Cholesterol, consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, - fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides, - complexing agents such as EDTA, NTA, ß-alanine diacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl carbonates, carbonates, hydrates , Guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate as well as PEG-3 distearate, pigments, stabilizing agents for hydrogen peroxide and other oxidizing agents, blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. B. Kh. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The agents according to the invention preferably contain the dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the dye precursors into a powdery or tablet-like formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a C 1 -C ₄ alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain further organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. According to the invention, however, the oxidation coloring agent can also be applied to the hair together with a catalyst which oxidizes the dye precursors, e.g. activated by atmospheric oxygen. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

Suitable enzymes are, for example, peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific therefor, for example pyranose oxidase and for example D-glucose or galactose, glucose oxidase and D-glucose, glycerol oxidase and glycerol, Pyruvate oxidase and pyruvic acid or its salts, Alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and its salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and arino acids.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. It is particularly preferred to use the hair dye in a weakly alkaline environment. Application temperatures can range between 15 and 40 ° C. After an exposure time of generally 5 to 45 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

In the case of hair that is difficult to dye, the preparation with the dye precursors can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the skin is rinsed and, if necessary, re-shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to bring about better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, air oxidation is initially sought, with the applied one. Agent preferably has a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.

A second subject of the present application is the use of the m-phenylenediamine derivatives according to the invention for dyeing keratin fibers. A third object of the present invention is a process for dyeing keratin fibers, in which a hair dye according to the invention is applied to the fibers and rinsed off again after an exposure time.

A fourth object of the present invention is an m-phenylenediamine derivative of the general formula (I) as described above. 2 - ({3 - [(2-Hydroxyethyl) amino-5-methylphenyl} amino) ethanol is a very particularly preferred compound of the formula (I).

A fifth object of the present invention is an intermediate synthesis selected from the group consisting of 2-chloroethyl-3 - {[(2-chloroethoxy) carbonyl] amino} -5-methylphenylcarbamate and 3- [3-methyl-5- (2nd -oxo-l, 3-oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one.

The invention is illustrated by the examples below.

1. Syntheses

1.1 2 - ({3 - [(2-Hydroxyethyl) amino-5-methylphenyl} amino) ethanol

1.1.1 4-methyl-2,6-dinitroaniline

1 liter of nitric acid (90%) was placed in a 2 liter three-necked flask. At 20 ° C., 105 g of 4-methylacetanilide were added in portions, and after the addition had ended, the mixture was poured onto about 1 l of ice. The precipitate formed was filtered off with suction and washed neutral with water, suspended in 670 ml of 50% sulfuric acid and stirred at 90 ° C. for 1 h. The mixture was allowed to cool to 20 ° C., filtered and washed immediately with ice water. The mixture was then dried overnight under reduced pressure.

Melting point: 171-173 ° C Yield: 82 g (59%)

1.1.2 1-methyl-3,5-dinitrobenzene

14 g of 4-methyl-2,6-dinotroaniline were placed in 700 ml of absolute ethanol and mixed with 70 ml of concentrated sulfuric acid. After adding 14 g of sodium nitrite, the mixture was heated under reflux and 2.5 ml of water was added. After 1 h another 27 g of sodium nitrite were added and stirring was continued for 1 h under reflux. Subsequently, the batch was poured into 1 liter of ice water, the precipitated product was filtered off and dried overnight under reduced pressure.

Melting point: 86 - 89 ° C

Yield: 11 g (86%)

1.1.3 3-Amino-5-methylphenylamine

6 g of l-methyl-3,5-dinitrobenzene dissolved in 180 ml of ethanol + 20 ml of water were mixed with 0.1 g of Pd / C 5% and hydrogenated at room temperature for 6 h at atmospheric pressure (hydrogen). The catalyst was filtered off and the mixture was evaporated to dryness.

Yield: 3.6 g (89%)

1.1.4 2-Chloroethyl 3 - {[(2-chloroethoxy) carbonyl] amino} -5-methylphenyl carbamate

19.5 g of 3-amino-5-methylphenylamine and 51 g of calcium carbonate were placed in 0.5 l of dioxane and heated to 90 ° C. 60 g of 2-chloroethyl chloroformate were then added over the course of 15 minutes, and the mixture was stirred at this temperature for a further 4 hours. The mixture was then allowed to cool and the mineral salts were filtered off. The filtrate was poured onto ice water and extracted several times with ethyl acetate. The mixture was then evaporated to dryness on a Rotavapor, giving a waxy substance.

Yield: 46 g (86%)

1.1.5 3- [3-Methyl-5- (2-oxo-l, 3-oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one 200 ml of sodium hydroxide solution (20%) were introduced and heated to 45 ° C. 46 g of 2-chloroethyl 3 - {[(2-chloroethoxy) carbonyl] amino} -5-methylphenylcarbamate were then added in portions, the mixture was diluted with 200 ml of dioxane and the mixture was stirred at 45 ° C. for a further 4 h. The mixture was then poured onto ice and neutralized with hydrochloric acid. The precipitated product was filtered off with suction and dried overnight under reduced pressure.

Melting point: 195 - 197 ° C

Yield: 19 g (53%)

1.1.6 2- ({3 - [2-Hydroxyethyl) amino] -5-methylphenyl} amino) ethanol

200 ml of 20% NaOH were introduced and heated to reflux. 48 g of 3- [3-methyl-5- (2-oxo-l, 3-oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one were added in portions, the mixture was diluted with 200 ml of dioxane and heated for a further 8 h under reflux. The mixture was allowed to cool to room temperature overnight and was added to 1.5 l of ice water. The mixture was then neutralized with HC1, the aqueous phase was saturated with NaCl and extracted several times with ethyl acetate. After drying over sodium sulfate, the mixture was concentrated on a Rotavapor and then distilled in a Kugelrohr.

Yield: 8 g (53%)

2. Discolorations

2.1 Carrying out the experiment

For the production of the coloring cream, 50 g of a cream base were weighed into a 250 ml beaker and melted at 80 ° C. The cream base used had the following composition:

Hydrenol ^® D ¹ 17.0% by weight

Lorol ^® tech. ² 4.0% by weight

Texapon ^® NSO ³ 40.0% by weight

Dehyton ^® K ⁴ 25.0% by weight

Eumulgin ^® B2 ⁵ 1.5% by weight

Water 12.5% by weight

¹ C _16- ι ₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) ² Ci ₂ -ι ₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis) ³ lauryl ether sulfate, sodium salt (approx. 27.5% active substance ; INCI name: Sodium Laureth Sulfate) (Cognis) ⁴ N, N-dimethyl-N- (C ₈ .ι ₈ -kokosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis) ⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

In each case 1/400 mol of the developer or coupler component was suspended separately in distilled water or dissolved under heating. Then ammonia (<1 ml; 25% ammonia solution) was added until the pH was between 9 and 10.

The dissolved dye precursors were worked into the hot cream one after the other. The mixture was then made up to 97 g with distilled water and filled with Ammonia adjusted a pH of 9.5. After filling up to 100 g with distilled water, the mixture was stirred cold (<30 ° C.), a homogeneous cream being formed.

Unless otherwise noted, 25 g of coloring cream were mixed with 25 g of the following oxidizing agent preparation for the colorations.

Dipicolinic acid 0.1% by weight

Sodium pyrophosphate 0.03% by weight

Turpinal ^® SL ⁶ 1.50% by weight

Texapon ^® N28 ⁷ 2.00% by weight

Acrysol ^® 22 ⁸ 0.60% by weight

Hydrogen peroxide, 50% 12.0% by weight

Sodium hydroxide solution, 45% 0.80% by weight

Water ad 100 l-hydroxyethane-l, l-diphosphonic acid (approx. 58 - 61% active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Solutia) lauryl ether sulfate sodium salt (at least 26.5% active substance content; INCI name: Sodium Laureth Sulfate) (Cognis) acrylic polymer (approx. 29.5 - 30.5% solids in water; INCI name: Acrylates / Steareth-20 methacrylate copolyme)

A strand of hair (80% gray; 330 mg to 370 mg in weight) was added to each of the mixtures thus obtained. The mixtures and the strands of hair were then each placed on a watch glass and the strands of hair were well embedded in the coloring creams. After 30 minutes (± 1 minute) of exposure at room temperature, the strands of hair were removed and washed with an aqueous Texapon ^® EVR solution until the excess color was removed. The strands of hair were air-dried and their shade was determined and noted under the daylight lamp (color testing device HE240A) (Taschenlexikon der Farben, A. Kornerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag; Zurich, Göttingen) , Lauryl ether sulfate sodium salt with special additives (approx. 34 to 37% active substance content; INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-1 ^' 0) (Cognis)

The results obtained in the coloration tests are shown in the table below.

For comparison ^' staining was carried out with 2 - ({3- (2-hydroxyethyl) aminophenyl} amino) ethanol, a compound which is described in DE-A-29 27 870 and apart from the absence of the methyl group on the benzene nucleus of the compound ( 1) corresponds.

2.2 Colorings

El = p-toluenediamine x H ₂ SO ₄ E2 = 2,4,5,6-tetraaminopyrimidine x H ₂ SO ₄ E3 = p-aminophenol E4 = 4,5-diamino-l- (2-hydroxyethyl) pyrazole x H ₂ SO ₄ E5 = 2- (2,5-diaminophenyl) ethanol x H ₂ SO ₄ E6 = 4-amino-3-methylphenol

E7 = 4-amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol x 2 HCl

E8 = NN-bis (2-hydroxyethyl) p-phenylenediamine

In contrast to the colorations with the coupler component of the prior art, the colorations with the coupler component according to the invention are clearly shifted into the red area.

Claims

claims

1. Agent for coloring keratin fibers, in particular human hair, containing at least one m-phenylenediamine derivative of the general formula (I) in a cosmetically acceptable carrier as a coupler component

(0 with the meaning

R '. , , R ^{4 is} independently H, Cι _-6 alkyl, C _Σ - _ö Ηydroxyalkyl, C _2-6 alkoxyalkyl, C ₂ - ₆ aminoalkyl, C _3- ιo-alkylaminoalkyl, dialkylaminoalkyl C _{4- 2,} with the proviso that at least one of the radicals R 1, r R.2 R ³ , R ^{4 is} different from H,

R ^5, R ⁶ are independently H, C _1-6 alkyl, C _1- 6 hydroxyalkyl, C 2-6 alkoxyalkyl, whereby one of the radicals R 5, _D R6 -OH, Cι _-6 alkoxy, - NH ₂ , -NHR, -NR ₂ with R in each case independently of one another can optionally be OH-substituted C 1 -C alkyl, or salts thereof.

2. Composition according spoke 1, characterized in that in the phenylenediamine derivative of the general formula (I) R ¹ , R ² , R ³ , R ⁴ independently of one another are H, C _1- alkyl or C _2-4 -hydroxylalkyl.

3. Composition according spoke 2, characterized in that in the phenylenediamine derivative of the general formula (I) R ¹ and R ^{3 are} hydrogen and R ² and R ^{4 are} hydrogen or C ₂ . _4- Hydroxyalkyl mean.

4. Composition according spoke 3, characterized in that in the phenylenediamine derivative of the general formula (I) R ¹ and R ^{3 are} hydrogen and R ² and R ⁴ -CH ₂ -CH ₂ OH.

5. Composition according to one of claims 1 to 4, characterized in that in the phenylenediamine derivative of the general formula (I) R ⁵ , R ⁶ independently of one another are hydrogen, C _1-4 -alkyl or C _1-4 -hydroxyalkyl.

6. Composition according to claim 5, characterized in that in the phenylenediamine derivative of the general formula (I) R ^{5 is} hydrogen and R ^{6 is} hydrogen or Cι _-3 - alkyl.

7. Composition according to claim 6, characterized in that in the phenylenediamine derivative of the general formula (I) R ^{5 is} hydrogen and R ^{6 is} methyl.

8. Composition according to one of claims 1 to 7, characterized in that it contains at least one developer component.

9. Composition according to one of claims 1 to 8, characterized in that it contains at least one further coupler component.

10. Agent according to one of claims 1 to 9, characterized in that it further contains at least one substantive dye.

11. A composition according to claim 10, characterized in that the substantive dye is cationic.

12. A process for dyeing keratin fibers, in which an agent according to one of claims 1 to 11 is applied to the fibers and rinsed off again after an exposure time.

13. Use of m-phenylenediamine derivatives of the general formula (I), as defined in one of claims 1 to 7, for coloring keratin fibers, in particular human hair.

14. phenylenediamine derivative of the general formula (I) as defined in one of claims 1 to 7.

15. 2- ({3 - [(2-hydroxyethyl) amino-5-methylphenyl} amino) ethanol

16. Intermediate synthesis selected from the group consisting of 2-chloroethyl-3- {[(2-chloroethoxy) carbonyl] amino} -5-methylphenyl carbamate and 3- [3-methyl-5- (2-oxo-1,3 oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one.