EP1748822A1 - M-phenylene diamine coupling components - Google Patents

Abstract

Disclosed is a substance for dyeing keratin fibers, particularly human hair, containing at least one m-phenylene diamine derivative of general formula (I) as a coupling component in a cosmetically acceptable carrier. In said formula (I), R1, R2, R3, R4 independently represent H, C1-6 alkyl, C2-6 hydroxyalkyl, C2-6 alkoxyalkyl, C2-6 aminoalkyl, C2-10 alkylaminoalkyl, C3-12 dialkylaminoalkyl; R5, R6 independently represent C1-6 alkyl which is optionally substituted by -OH, optionally OH-substituted C1-4 alkoxy, -NH2, - NHR, or -NR2, R independently representing optionally OH-substituted C1-4 alkyl; R7 represents H, halogen or C1-6 alkoxy, C1-6 alkyl which are optionally substituted by -OH, optionally OH-substituted C1-4 alkoxy, -NH2, - NHR, -NR2, except on the C atom located closest to the aromatic core, R independently representing optionally OH-substituted C1-4 alkyl; X represents H, halogen, C1-6 alkoxy which is optionally substituted by -OH or C1-4 alkoxy; or salts thereof.

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 a part of 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, 2-aminomethyl-4-aminophenol, 2 -Hydroxy-4,5,6-triaminopyrimidine, 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. Suitable coupler substances are in particular 1-naphthol, 1, 5-, 2.7- and 1.7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl-3-methyl-pyrazolone-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.

Mono-alkyl-substituted 1,3-phenylenediamines have long been used as a coupler component in oxidative hair colors. For example, 2,4-diaminotoluene has been used in the past for many years, for example as a blue coupler for p-phenylenediamine and p-tolylenediamine. Di-alkyl-substituted 1,3-phenylenediamines have also been used as a coupler component in oxidative hair colors.

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. It was therefore an object of the present invention to develop new coupler components which meet the requirements imposed on oxidation dye precursors, also with regard to the toxicological and dermatological properties, and which enable dyeings in a wide color spectrum 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 in particular enable the production of red tones with good fastness properties.

The invention therefore firstly relates to compositions for dyeing 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 coupling component

with the meaning

R \ R ^2, R ^3, R ⁴ are independently H, Cι _-6 alkyl, C ₂ - ₆ hydroxyalkyl, C _2-6 alkoxyalkyl, C _2-6 aminoalkyl, C -ι ₀ alkylaminoalkyl, C ₃ -ι ₂ -dialkylaminoalkyl,

R ⁵ , R ⁶ independently of one another. ₆ alkyl, which is optionally substituted by:

-OH, optionally OH-substituted Cι _-4 -alkoxy, -NH ₂ , - NHR, -NR ₂ with R each independently of one another optionally OH-substituted Cι _-4 -alkyl, R ⁷ is H, halogen, or _{C] -6} alkoxy, Cι _-6 alkyl, optionally substituted on the aromatic nucleus other than the nearest carbon atom are substituted by:

-OH, optionally OH-substituted Cι _-4 -alkoxy, -NH ₂ , - NHR, -NR ₂ with R each independently, if appropriate, OH-substituted C ^ alkyl,

XH, halogen, Cι _-6 - alkoxy, which is optionally substituted by -OH or Cι _-4 - alkoxy,

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 A to C for the _ό mentioned as substituents in the compounds of the invention Ci- alkyl, preferably -C ₄ alkyl groups which may be linear or branched, the groups methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl. Ethyl and methyl are preferred alkyl groups. A hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group can be mentioned as the preferred Ci to C ₆ - (mono) hydroxyalkyl group. A 2-hydroxyethyl group is particularly preferred. C _2-6 alkoxyalkyl radicals have a total of 2 to 6 carbon atoms, which are distributed over the alkoxy and the alkyl radical. It can so that there are up to 5 carbon atoms in the alkoxy or alkyl radical. It is preferably a Cι. ₃ -alkoxy-Cι.3-alkyl radical, particularly preferably C1. ₂ -alkoxy-C ₁ . ₂ - alkyl group. Both the alkoxy and the alkyl radical can be linear or branched. They are preferably linear. C2- ₆ -aminoalkyl, preferably C _2-4 -aminoalkyl, C _2- ι ₀ -Alkylaminoalkylreste, C _2-6 -Alkylaminoalkylreste and preferably C ₃ i ₂ - dialkylaminoalkyl, preferably C _3-9 -Dialkylaminoalkylreste may each be linear or branched Have 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.

If radicals are optionally substituted, depending on the number of carbon atoms in the alkyl or alkoxy radical, there may preferably be 1 to 3, particularly preferably 1 or 2, in particular one substituent. R ⁵ , R ⁶ , R ⁷ and X may have substituents, some of which may in turn be substituted by -OH. Preferably only one of these further OH substituents is present. C _-4 alkyl and C _M alkoxy radicals are in turn linear or branched, preferably linear, and particularly preferably ethyl or methyl. If one of the radicals R ¹ to R ⁷ and X contains a hydroxyl group bonded to an alkylene radical, the hydroxyl group is preferably terminal and the alkylene radical is linear. A hydroxyethyl radical is therefore preferably a 2-hydroxyethyl radical. If the rest of R ^{7 is} a Cι. ₆ -alkoxy or Ci- ₆ -alkyl radical, this may be substituted, but not on the C atom which is closest to the aromatic nucleus to which the radical R ^{7 is} attached.

Halogen is generally F, Br, CI or I, preferably CI or Br.

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, the m-phenylenediamine derivative of the general formula (I) contains a maximum of a further four oxygen atoms, preferably a maximum of a further two 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, C _-4 alkyl or C _2-4 hydroxyalkyl. R ¹ and R ^{3 are} particularly preferably hydrogen and R ² and R ^{4 are} hydrogen or C _2-4 -hydroxyalkyl.

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

In one embodiment of the invention, X is preferably hydrogen.

According to one embodiment of the invention, R ^{7 is} preferably hydrogen or C alkyl.

According to a particularly preferred embodiment of the invention, R ¹ , R ² , R ³ , R ⁴ , X are hydrogen and R ⁵ , R ^{6 is} methyl. R ⁷ particularly preferably denotes hydrogen or methyl.

According to a further particularly preferred embodiment of the invention, R ¹ , R ³ , X, R ^{7 are} hydrogen, R ⁵ , R ^{6 is} methyl 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, e.g. 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 according to 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 and the specialist book 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 hydroxyl 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

wherein G ¹ represents a hydrogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C _r to C ₄₎ - alkoxy (d- to C ₄ ) -alkyl, a 4'-aminophenyl or a Ci- to C -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G ² represents a hydrogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (Ci to C ₄₎ - alkoxy (Cι- to C ₄ ) alkyl radical or a C 1 -C ₄ -alkyl radical which is substituted by a nitrogen-containing group; G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a Cr to C ₄ alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Ci to C ₄ - Hydroxyalkoxy, a Cp to C ₄ acetylaminoalkoxy, a C _\ to C mesylaminoalkoxy or a C to C ₄ carbamoylaminoalkoxy; G ^ 4 represents a hydrogen atom, a halogen atom or a Cr to 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, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the Cr to C 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 Cr to C ₄ alkoxy radicals are, for example, a methoxy or an ethoxy group. Furthermore, 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-hydroxy ethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ - polyhydroxyalkyl group is 1, 2-dihydroxyethyl. 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 the formula (E1) are in particular the amino groups, Cr to C monoalkylamino groups, Cr to C ₄ dialkylamino groups, Cr to C ₄ trialkylammonium groups, Cr to C monohydroxyalkylamino groups, 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- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2 -methylaniline, 4-N, N-bis- (ß-hydroxyethyl) -amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-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-yl) propyl] amine, which may also be phenyl or Cι _-6 - alkylphenyl instead of 3-methylphenyl, 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 and 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 C _\ - to C ₄ -alkyl radical, by a Cr to C ₄ - hydroxyalkyl radical and / or by a bridging Y. or which is optionally part of a bridging ring system, the bridge Y represents an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which are interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms can and may be substituted by one or more hydroxyl or Cr to C ₈ alkoxy radicals, or a direct bond, G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a Cr to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl, a C ₂ to C ₄ polyhydroxyalkyl, a Cr to C ₄ aminoalkyl or a direct connection to the bridging Y, G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are independent from each other for a hydrogen atom, a direct bond to the bridging Y or a Cr to C ₄ alkyl radical, with the provisos that the compounds of the formula (E2) only have one bridging Kung Y contain per molecule and the compounds of 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 (ß-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 (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -l, 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) -l, 4-diazacycloheptane and l, 10-bis- (2 ', 5'-diaminophenyl) -l, 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 Cr to C alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) -alkyl radical, a C to C ₄ -aminoalkyl radical, a hydroxy- (Cr to C ₄ ) -alkylamino radical, a Cr to C ₄ -hydroxyalkoxy radical, a Cr to C -hydroxyalkyl- (Cι-to C ₄ ) -aminoalkyl radical or a (di-Cr to C ₄ alkylamino) - (Cr to C ₄ ) alkyl radical, and G ¹⁴ represents a hydrogen or halogen atom, a Cr to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, one C2 to C ₄ polyhydroxyalkyl, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl, a Cr to C ₄ aminoalkyl or a Cr to C ₄ cyanoalkyl, G ¹⁵ represents hydrogen, one d to C ₄ alkyl, a Cr to C ₄ monohydroxyalkyl, a C ₂ to C ₄ polyhydroxyalkyl, a phenyl or a benzyl, 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 patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine , 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-triaminopyrirnidine, 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-l - (4 ¹ - 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-l- (β-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-dimethylpyraz ol, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino-4- (ß-hydroxyethyl) - amino-l-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 that there is a tautomeric equilibrium:

where: G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a Cr to C alkyl radical, an aryl radical, a Cr to C hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical a ( Cr to C ₄ ) alkoxy- (Cr to C ₄ ) - alkyl radical, a Cr to C ₄ -aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (Cr to C) alkylamino - (Cj to C) alkyl radical, a di - [(Cr to C) 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 C _\ - to C ₄ - Hydroxyalkyl or a di (Cr to C ₄ ) - [hydroxyalkyl] - (Cr to C ₄ ) - aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a Cr to C ₄ alkyl radical, an aryl radical, a Cr to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cj to C ₄ aminoalkyl radical, a (Cr to C ₄ ) alkylamino (Cr to C ₄ ) alkyl radical, a di- [ (d- to C ₄ ) alkyl] - (Cr to C) - aminoalkyl radical, where the dialkyl radicals optionally form 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, an amino, ad- to C ₄ -alkyl or di- (d- to C ₄ -hydroxyalkyl) -amino, 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 equal to 2 n has the value 0 and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ 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- [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine; 3-aminopyrazole [l, 5-a] -ρyrimidin-7-ol; 3-aminopyrazole- [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-aminopyrazole [l, 5-a] pyrimidine-3-ylamino) ethanol; 2 - [(3-aminopyrazole [l, 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol; 2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol; 5,6-dimethylpyrazole [l, 5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazole [l, 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-Dimethyl-3-aminophenol, 3-trifluoroacetylamino-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, 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, onomethyl 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-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-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-aminobenzomorpholine, quinoxaline derivatives such as 6-methyl 1, 2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-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- (2nd '- 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, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - {({3- [2- Hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [2-hydroxyethyl) amino] -4-methoxy-5-methylpheny 1} 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: p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, 1 - (2-hydroxyethyl) -2,5-diaminobenzene, 1 - (2-hydroxyethyl) -4,5-diaminopyrazole and bis- (2-hydroxy-5 -aminophenyl) methane in each case in combination with the compounds from the examples, in particular with 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} 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,

(Ha) R '

in which independently of one another - R ¹ stands for hydrogen, a C 1 -C ₄ -alkyl group or a C] -C ₄ -hydroxy-alkyl group, - R ² stands for hydrogen or a -COOH group, the -COOH group can also be present as a salt with a physiologically compatible cation,

R stands for hydrogen or a C ₄ alkyl group, R ⁴ stands for hydrogen, a C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₄ alkyl group, and R ⁵ represents one of the groups mentioned under R ⁴ , as well as 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 especially 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 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 Cι- C ₄ alkyl group, and R ⁵ stands for 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 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 used 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 another preferred embodiment of the present invention, the colorants according to the invention can contain one or more direct 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 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2 - (2'-Hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) arnino-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'-carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-l, 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. Particularly preferred are (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 with 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 ^~

Cf

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by 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 which are sold under the brand Arianor® ^® are, according to the invention also very particularly preferred cationic direct dyes.

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, in the hair colorants according to the invention, due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or must be excluded for other reasons, for example toxicological ones. 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 colorants according to the invention can furthermore contain all active substances, 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 carbon atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates 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 θ) _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 -37 23 354, sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, esters of tartaric acid and citric acid with alcohols, the addition products of about 2-1 5 molecules of ethylene oxide and / or propylene oxide on 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 C ₈ -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, _Ci2-C22 fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide with glycerol, _C8-C22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof and addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated 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 using so-called "oxo alcohols" 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 Cg and Cio-alkyl groups, essentially from C] ₂ - and Cι ₄ -alkyl groups, essentially from C ₈ - to Ci ₆ -alkyl groups or essentially from Cι - to Cι ₆ alkyl groups.

Any mono- or oligosaccharides can be used as the sugar building block Z. Usually sugar with 5 or 6 carbon atoms and the corresponding Oligosaccharides 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 according to 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 -SOs ^ 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 cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium 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.

Also particularly suitable as co-surfactants are a pholytic surfactants. Ampholytic surfactants are understood to mean those surface-active compounds which addition to a C-Cι _g - alkyl or acyl group, contain at least one free amino group and contain at least one -COOH or _-SO3H group and are capable of forming inner salts. 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 the N-coconut alkylaminopropionate, the coconut acylaminoethylaminopropionate and the C _2- i 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, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names quatemium-27 and quatemium-83. 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 invented According to the invention, a particularly suitable compound from this group of substances is stearamidopropyldimethylamine, which is commercially available under the Tegoamid ^® S 18 brand.

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 Coming; 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 polydimethylsiloxane, 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. By 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 as catalysts be used. 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, polysiloxanes with quaternized cellulose ethers , Dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinylalphamido-methylethyl alcohol, zamperidyl chloride, for example, aminotrophonyl polymers, for example, amido-methylammonyl chloride, zwitterionyl chloride Copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid-C opolymers, 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 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 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, glycerol and diethylene glycol, active substances which improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, 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 olamines, zinc omadines and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines to adjust the pH, such as customary acids, especially edible acids and bases, active ingredients such as AUantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol, vitamins, provitamins and vitamin precursors, especially 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, white doe, linden flowers, almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, Apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosemary, Birch, Mallow, Cuckoo Flower, Quendel, Sc oatmeal, 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, β-alanine diacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonate , 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 and 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, contain.

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, for example, 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 activates the oxidation of the dye precursors, for example by atmospheric oxygen. Such catalysts are, for example, 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 e.g. Peroxidases, which can significantly increase the effects 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 for this, e.g. Pyranose oxidase and e.g. D-glucose or galactose, glucose oxidase and D-glucose, glycerol oxidase and glycerol, pyruvate oxidase and pyruvic acid or their salts, alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and their salts, tyrosinase -Oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino 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. The washing up with a shampoo is not necessary if a carrier with a high surfactant content, e.g. a coloring shampoo, has been used.

Particularly 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 supposed 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 aimed for, the agent applied preferably having 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) with the meaning R ¹ , R ³ , hydrogen, R ⁷ hydrogen or methyl, X hydrogen or methoxy, R ⁵ , R ⁶ methyl and R ² , R ⁴ -CH ₂ -CH ₂ OH.

A fifth object of the invention are the intermediates 4-methoxy-5,6-dimethyl-1,3-diaminobenzene, 2-chloroethyl 5 - {[(2-chloroethoxy) carbonyl] amino} -2-methoxy-3,4-dimethylphenylcarbamate , 3- [2-methoxy-3,4-dimethyl-5- (2-oxo-1,3-oxazolidin-3-yl) phenyl] -1, 3-oxazolidin-2-one, 2-chloroethyl-3- {[(2-chloroethoxy) carbonyl] amino} -4,5-dimethylphenyl carbamate and 3- [2,3-dimethyl-5- (2-oxo-l, 3-oxazolidin-3-yl) phenyl] -l , 3-oxazolidin-2-one. The invention is illustrated by the examples below.

embodiments

1. Syntheses

1.1 1, 3 -Diamino-2,4,5 -trimethylbenzene

1.1.1 2-bromo-3,4,6-trimethylaniline

28.4 g of 2,4,5-trimethylaniline dissolved in 100 ml of 1,1,1-trichloroethane were placed in a 250 ml three-necked flask at 0-5 ° C., and 33.6 g of bromine dissolved in 25 were added dropwise at this temperature ml of trichloroethane. The mixture was stirred for 2 h and then left to stand overnight. The brown suspension obtained was poured into a mixture of 100 ml of dilute NaOH and 170 ml of water, 1 g of sodium sulfite was added and the mixture was stirred for 1 h. The mixture was then extracted several times with MTBE. The combined ether extracts were washed with water, dried over sodium sulfate and evaporated to dryness overnight. The brown mass (41 g) thus obtained crystallized after a few days and was recrystallized again from 30 ml of water and 90 ml of ethanol and dried under reduced pressure overnight.

Melting point: 58-66 ° C

Yield: 18 g (40%) 1.1.2 2-Bromo-5-nitro-3,4,6-trimethylaniline

54 ml of concentrated sulfuric acid were placed in a 250 ml three-necked flask. At 0-10 ° C, 17.1 g of 2-bromo-3,4,6-trimethylaniline were added in portions. A mixture of 5.6 g of nitric acid (D = 1.52) and 18 ml of concentrated sulfuric acid was then added dropwise at 0-5 ° C. over 25 minutes. The mixture was left to stir at this temperature for 2 h and then poured onto ice water. The resulting precipitate was filtered off, washed neutral with water and then dried under reduced pressure.

Melting point: 109-142 ° C

Yield: 12.3 g (59%)

1.1.3 1, 3-diamino-2,4,5-trimethylbenzene dihydrochloride

11.7 g of 2-bromo-5-nitro-3,4,6-trimethylaniline dissolved in 300 ml of ethanol were mixed with 1 g of Pd / C, 5% and hydrogenated at 50 ° C. for 6 hours at 50 bar hydrogen pressure in an autoclave , The catalyst was then filtered off and concentrated to dryness. The residue was dissolved in 50 ml of dilute NaOH + 100 ml of water and extracted several times with MTBE. After the combined ether phases had dried, the mixture was concentrated and then distilled in a bulb tube. The 2.7 g of semicrystalline material thus obtained were dissolved in 20 ml of dilute HCL + 20 ml of EtOH, and the mixture was evaporated almost to dryness. The precipitated crystal slurry was filtered off and dried under reduced pressure overnight.

Yield: 2.2 g (33%) 1.2. 1,3-diamino-5,6-dimethylbenzene

1.2.1 3-Nitro-5,6-dimethylaniline

270 ml of concentrated sulfuric acid were placed in a 1 liter three-necked flask. 34 g of 2,3-dimethylaniline were added in portions at 0-10 ° C. A mixture of 15 ml of nitric acid (D = 1.52) and 45 ml of concentrated sulfuric acid was then added dropwise at -10 ° C. over 45 minutes. The mixture was left to stir at -10 to 0 ° C. for 1 h and then poured onto ice water. The resulting precipitate was filtered off, washed neutral with water and then dried under reduced pressure overnight.

Melting point: 98-104 ° C

Yield: 12.8 g (28%)

1.2.2 1, 3-diamino-5,6-dimethylbenzene

12.8 g of 3-nitro-5,6-dimethylaniline dissolved in 280 ml of ethanol + 20 ml of water were mixed with 0.1 g of Pd / C, 5% and hydrogenated at room temperature for 2 h at atmospheric pressure (hydrogen). The catalyst was filtered off and the mixture was evaporated to dryness.

Yield: 8.2 g (33%) 1.3 2- ({5 - [(2-hydroxyethyl) amino] -2-methoxy-3, 4-dimethylpheny 1} amino) ethanol

1.3.1 (2,3-dimethyl-4,6-dinitrophenyl) methyl ether

50 ml of fuming nitric acid were introduced at 5 ° C., and 10 g of 2,3-dimethylanisole were added dropwise with stirring. The mixture was stirred for 2 h and then poured onto ice, the precipitate was filtered off and washed with plenty of water. It was then washed neutral with sodium carbonate solution and water and dried in vacuo overnight.

Yield: 10.3 g (62%). Melting point: 58-62 ° C

1.3.2 4-methoxy-5,6-dimethyl-1,3-diaminobenzene

100 g (2,3-dimethyl-4,6-dinitrophenyl) methyl ether, 1.5 l ethanol, 100 ml water and 2 g Pd / C (5%) were placed in the autoclave and at 50 ° C with 50 bar Hydrogen pressure hydrogenated for 12 h. The mixture was then allowed to cool, the catalyst was filtered off and the mixture was evaporated to dryness on a Rotavapor.

Yield: 67 g (91%) melting point: 104-108 ° C 1.3.3 2-Chloroethyl 5 - {[(2-chloroethoxy) carbonyl) amino} -2-methoxy-3,4-dimethylphenyl carbamate

65 g of 4-methoxy-5,6-dimethyl-l, 3-diaminobenzene and 122 g of calcium carbonate were placed in 11 dioxane and heated to 90 ° C. 141 g of 2-chloroethyl chloroformate were 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 the precipitated product was filtered off (light brown crystals). It was then dried in vacuo.

Yield: 143 g (97%)

Melting point: 158-160 ° C

1.3.4 3- [2-methoxy-3,4-dimethyl-5 - (2-oxo-1,3-oxazolidin-3-yl) phenyl] -1,3-oxazolidin-2-one

200 ml of sodium hydroxide solution (20%) were introduced and heated to 45 ° C. 143 g of 2-chloroethyl 5 - {[(2-chloroethoxy) carbonyl] amino} -2-methoxy-3,4-dimethylphenylcarbamate 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 2 h , After stirring overnight at room temperature, the mixture was poured onto ice and neutralized with hydrochloric acid. The mixture was extracted several times with ethyl acetate and concentrated to dryness in vacuo.

Yield: 49 g (43%)

1.3.5 2- ({5- [(2-Hydroxyethyl) amino] -2-methoxy-3, 4-dimethylphenyl} amino) ethanol

200 ml of sodium hydroxide solution (20%) were introduced and heated to 90-100 ° C. 49 g of 3- [2-methoxy-3,4-dimethyl-5- (2-oxo-l, 3-oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one dissolved in 200 ml of dioxane added dropwise, and the mixture was left at this temperature for a further 2 h stir. After cooling overnight to room temperature, 1.5 l of ice water were added. It was then neutralized with HCl and extracted several times with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated on a Rotavapor. Then distilled in a Kugelrohr.

Yield: 9.2 g (23%)

1.4 2 - ({3 - [(2-Hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol

1.4.1 2-Chloroethyl 3 - {[(2-chloroethoxy) carbonyl] amino} -4,5 -dimethylphenyl carbamate

33 g of 5,6-dimethyl-l, 3-diaminobenzene and 77 g of calcium carbonate were placed in 0.5 l of dioxane and heated to 90 ° C. 90 g of 2-chloroethyl chloroformate were 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 into ice water and the precipitated product was filtered off (pink crystals). It was then dried in vacuo.

Yield: 67 g (80%)

Melting point: 106 - 108 ° C

1.4.2 3- [2,3-Dimethyl-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. 59 g of 2-chloroethyl 3 - {[(2-chloroethoxy) carbonyl] amino} -4,5-dimethylphenylcarbamate 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 2 h. After stirring overnight at room temperature, the mixture was poured onto ice and neutralized with hydrochloric acid. The precipitated product was suction filtered and dried in vacuo overnight.

Yield: 45 g (86%)

Melting point: 206 - 207 ° C

1.4.3 2 - ({3- [2-Hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol

200 ml of sodium hydroxide solution (20%), 45 g of 3- [2,3-dimethyl-5- (2-oxo-l, 3-oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one and 200 ml of dioxane was stirred under nitrogen under reflux for 8 h. After cooling overnight to room temperature, 1.5 l of ice water were added. It was then neutralized with HCl and extracted several times with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated on a Rotavapor. Then distilled in a Kugelrohr.

Yield: 2.4 g (7%)

Melting point: 133 - 134 ° C

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 '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

Ci _ö -is fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) Ci ₂ -i ₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis) lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name : Sodium Laureth Sulfate) (Cognis) N, N-dimethyl-N- (C _{8- 18} -kokosamidopropy l) ammoniumacetobetain (ca. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis) cetyl stearyl 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 ⁹ 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) , ⁹ 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-10) (Cognis)

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

2.2 Colorings with 1,3-diamino-5,6-dimethylbenzene

2.3 Colorings with 1,3-diamino-2,4,5-trimethylbenzene dihydrochloride

2.4 Colorings with 2- ({5 - [2-hydroxyethyl) amino] -2-methoxy-3, 4-dimethylphenyl} ami-no) ethanol

2.5 Colorings with 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol

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 coupling component

with the meaning

R ', R ² , R ³ , R ⁴ independently of one another H, Cι _-6- alkyl, C _2-6 -hydroxyalkyl, C _2-6 -alkoxyalkyl, C _2-6 -aminoalkyl, C ₂ -ιo-alkylaminoalkyl, C _3- i ₂ -dialkylaminoalkyl,

R ^5, R ^{6 are} independently Cι _-6 alkyl which is optionally substituted by:

-OH, optionally OH-substituted Cι _-4 -alkoxy, -NH ₂ , - NHR, -NR ₂ with R each independently of one another optionally OH-substituted Cι _-4 -alkyl,

R 'is H, halo or Cι _-6 alkoxy, C ₁ - ₆ - alkyl, the carbon atom are substituted, except at the aromatic nucleus closest by:

-OH, optionally OH-substituted Cι _-4 -alkoxy, -NH ₂ , - NHR, -NR ₂ with R each independently, if appropriate, OH-substituted C ^ alkyl,

XH, halogen, Cι _-6 - alkoxy, which is optionally substituted by -OH or Cι _-4 - alkoxy, or salts thereof.

Agent according to claim 1, characterized in that in the phenylenediamine derivative ddeerr aallllggeemmeeiinneenn FFoorrmmeell ((II)) RR ¹ ,, RR " ² , R ³ , R ⁴ independently of one another denote H, C _-4 alkyl or C _2-4 hydroxyalkyl.

3. Composition according to claim 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- hydroxyalkyl.

4. Composition according to one of claims 1 to 3, characterized in that in the phenylenediamine derivative of the general formula (I) R ⁵ and R ⁶ independently of one another are Cι _-4 - alkyl.

5. Composition according to one of claims 1 to 4, characterized in that in the phenylenediamine derivative of the general formula (I) X is hydrogen.

6. Composition according to one of claims 1 to 5, characterized in that in the phenylenediamine derivative of the general formula (I) R ^{7 is} hydrogen or -CC ₄ alkyl.

7. Composition according to one of claims 1 to 6, characterized in that in the phenylenediamine derivative of the general formula (I) R ¹ , R ² , R ³ , R ⁴ , X are hydrogen and R ⁵ , R ^{6 is} methyl.

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

9. Composition according to one of claims 1 to 6, characterized in that in the phenylenediamine derivative of the general formula (I) R, R, hydrogen, R hydrogen or methyl, X hydrogen or methoxy, R ⁵ , R ⁶ methyl and R ² , R ⁴ -CH ₂ -CH ₂ OH mean.

10. Agent according to one of claims 1 to 9, characterized in that it contains at least two different m-phenylenediamine derivatives.

11. Agent according to one of claims 1 to 10, characterized in that it contains at least one developer component.

12. Composition according to one of claims 1 to 11, characterized in that it contains at least one further coupler component.

13. Composition according to one of claims 1 to 12, characterized in that it further contains at least one substantive dye.

14. Composition according to claim 13, characterized in that the substantive dye is cationic.

15. A process for dyeing keratin fibers, in which an agent according to one of claims 1 to 14 is applied to the fibers and rinsed off again after a contact time.

16. Use of m-phenylenediamine derivatives of the general formula (I), as defined in one of claims 1 to 9, for coloring keratin fibers, in particular human hair.

17. m-phenylenediamine derivative of the general formula (I) as defined in claim 9, or salt thereof.

18. 4-methoxy-5,6-dimethyl-1,3-diaminobenzene, 2-chloroethyl 5 - {[(2-chloroethoxy) carbonyl] amino} -2-methoxy-3,4-dimethylphenyl carbamate, 3- [2- Methoxy-3,4-dimethyl-5- (2-oxo-l, 3-oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one, 2-chloroethyl-3 - {[(2-chloroethoxy ) carbonyl] amino} -4,5-dimethylphenyl carbamate and 3- [2,3-dimethyl-5- (2-oxo-l, 3-oxazolidin-3-yl) phenyl] -l, 3-oxazolidin-2-one ,