WO2007071344A2 - Novel coupling constituents - Google Patents

Abstract

The invention relates to m-phenylenediamine derivatives of formula (I) and agents for dyeing keratin fibres, especially human hair, which contain as a coupling constituent at least one m-phenylenediamine derivative of formula (I) in a cosmetically acceptable carrier. In said formula (I), R1 represents a branched or unbranched C1-C8 alkyl group which can optionally carry one or more hydroxy groups, R2, R3 and R4 independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 monohydroxyalkyl group, a C2-C4 polyhydroxyalkyl group, a C1-C4 alkoxy group, a C1-C4 alkoxy (C1-C4) alkyl group or a halogene atom.

Description

 N ews C o p p o rc o m p o n t e n s "

The present invention relates to coloring agents for keratinous fibers containing specific m-phenylenediamine derivatives bearing an alkoxyphenoxy group, a process for coloring hair with these agents, and these m-phenylenediamine derivatives themselves.

For the dyeing of keratin fibers, in particular human hair, the so-called oxidation colorants play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.

The developer components are usually primary aromatic amines having a further, located in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives ,

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-pyrazolone-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-hydroxybenzyl) ethyl) -N, N'-bis (4-aminophenyl) -diamino-propan-2-ol.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used. 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, 1-phenyl-nyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1, 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. Good oxidation dye precursors are primarily intended to meet the following requirements: They must form the desired color shades in sufficient intensity and authenticity in the oxidative coupling. You must also have a good Aufziehvermögen on the fiber, especially in human hair no significant differences between strained and freshly regrowed hair may exist (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, eg permanent wave liquids. Finally, if applied as a hair dye, they should not stain the scalp too much and above all they should be safe in terms of toxicology and dermatology. Furthermore, the coloring achieved by bleaching should be easily removed from the hair, if it does not meet the individual wishes of each person and should be reversed.

But with a developer component or a special coupler / developer combination, it is usually not possible to obtain a natural color shade 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 are unproblematic in terms of toxicology and dermatology.

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

Surprisingly, it has now been found that specific m-phenylenediamine derivatives which carry an alkoxyphenoxy group satisfy the requirements imposed on coupler components to a high degree. The coupler components according to the invention allow, in particular with the developer components p-phenylenediamine, p-toluenediamine, 2- (.beta.-hydroxyethyl) -p-phenylenediamine and N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine intensive dyeings in the blue range.

A first subject of the present invention are therefore agents for coloring keratinic fibers, in particular human hair, containing in a cosmetically acceptable carrier as coupler component at least one m-phenylenediamine derivative of the formula (I)

in which

R ₁ , is a branched or unbranched C ₁ - to C ₆ -alkyl group which may optionally carry one or more hydroxyl groups,

R ₂ , R ₃ and R ₄ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -

Alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ alkoxy group, a C ₁ to C ₄ alkoxy C ₁ to C ₄ alkyl group or a

Halogen atom.

According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the oxidation dyes according to the invention are primarily suitable for dyeing keratin fibers, in principle, there is nothing to prevent their use in other fields, in particular in color photography.

Since the m-phenylenediamine derivatives according to the invention are amino compounds, the known acid addition salts can be prepared therefrom in the customary manner. All statements of this document and, accordingly, the scope claimed cover both the compounds present in free form and their water-soluble, physiologically tolerated salts. Examples of such salts are the hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, citrates and lactates. The hydrochlorides and the sulfates are particularly preferred.

Examples of the C ₁ - to C ₆ -alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl , n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl and 2,2-dimethylbutyl. Ethyl and methyl are preferred alkyl groups. Preferred C ₁ to C ₄ alkoxy groups are the methoxy and ethoxy groups. Furthermore, as preferred examples of a C ₁ to C ₄ monohydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ - Polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here.

The m-phenylenediamine derivatives of the formula (I) can be prepared by conventional organic methods. For example, reference is made at this point to the experimental procedures in the context of the embodiments.

The now claimed m-phenylenediamine derivatives of the formula (I) have not previously been described in the literature. However, some structurally related compounds are described in the literature. Thus, for example, EP-A1-1 mentions 149,575 compounds which have a further aromatic ring compared with the coupler components now claimed. However, these compounds can not fully convince in terms of the Aufziehvermögens and the Egalisierungsverhaltens.

According to the invention of the formula (I) may be m-phenylenediamine derivatives are preferred in which the substituent R ₁ is a branched or unbranched C ₁ - to C ₄ -monohydroxyalkyl group - to C ₄ alkyl group or a branched or unbranched C. ₁

According to the invention, m-phenylenediamine derivatives of the formula (I) have proved to be particularly preferred in which the substituent R _{1 is} a methyl group or a hydroxyethyl group.

It may be preferred according to the invention if the radical -OR _{1 is} in the 2'-position; likewise preferred may be m-phenylenediamine derivatives in which the radical -OR _{1 is} in the 3'-position; furthermore, m-phenylenediamine derivatives may be in which the radical -OR _{1 is} in the 4'-position. Furthermore, the compounds have proved to be preferred in which the radical R _{2 is} in the T position.

Furthermore, such m-phenylenediamine derivatives of the formula (I) have proved to be preferred in which the substituent R _{2 is} hydrogen.

Likewise preferred for the purposes of the present invention are m-phenylenediamine derivatives of the formula (I) in which the substituent R _{3 is} hydrogen.

Further preferred according to the present invention are m-phenylenediamine derivatives of formula (I), in which the substituent R ₄ is hydrogen. Very particular preferred m-phenylenediamine derivatives of the formula (I) according to the invention are 3-amino-4- (4-methoxyphenoxy) -phenylamine, 3-amino-4- (3-methoxyphenoxy) -phenylamine, 3-amino-4- (2-methoxyphenoxy) phenylamine, 3-amino-4- (4- (2-hydroxyethoxy) phenoxy) -phenylamine, 3-amino-4- (3- (2-hydroxyethoxy) phenoxy) -phenylamine and 3-amino-4- (2- (2 - hydroxyethoxy) phenoxy) phenylamine. The connections

3-Amino-4- (4-methoxyphenoxy) -phenylamine, 3-amino-4- (3-methoxyphenoxy) -phenylamine and 3-amino-4- (2-methoxyphenoxy) -phenylamine are most preferred according to the invention.

In addition to the m-phenylenediamine derivatives of the formula (I), the colorants according to the invention may further comprise at least one developer component.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ J -alkoxy) (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to 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 - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C _r to C ₄₎ alkyl radical or a C ₁ - to C ₄ alkyl radical substituted with a nitrogenous group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkylrest, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ - acetylaminoalkoxy, a C ₁ - to C ₄ - Mesylaminoalkoxyrest or a C ₁ - to C ₄ - carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group. Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C-dialkylamino, C ₁ - to C ₄ -Trialkylammoniumgruppen, C ₁ - to C ₄ - Monohydroxyalkylaminogruppen, 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 (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- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N , N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetyl aminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine and 5,8-Diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.

It may further 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 dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

wobei:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may optionally be substituted by one or more hydroxyl or C ₁ - 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 C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest or a direct connection to the bridge Y ₁

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 - to C ₄ -alkyl radical, with the proviso that the compounds of the formula (E2) contain only one bridging Y per molecule.

The substituents used in formula (E2) are defined according to the invention analogously to the above statements.

Preferred binuclear 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) tetramethylenediamine, N, N'-bis - (.beta. hydroxyethyl) -N, N'-bis (4-aminophenyl) -tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) -tetramethylenediamine, N.N'-diethyl-N, N'-bis- '-amino-S'-methylphenyO-ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'- Bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10 tetraoxadecane and its physiologically acceptable salts.

Very particularly preferred binuclear 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 its physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkyl group - (C ₁ - to C ₄₎ alkyl group a C ₁ - to C ₄ aminoalkyl radical, a hydroxy (Cr to _C4) alkylamino group, a Ci to C ₄ -Hydroxyalkoxyrest, a C ₁ - to C ₄ hydroxyalkyl (Crbis C ₄₎ aminoalkyl radical or a (di-C ₁ - to C ₄ -alkylamino) - alkyl (C _r to C _4), and

G ¹⁴ is a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy (C _r to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,

G ¹⁵ is hydrogen, C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom. The substituents used in formula (E3) are defined according to the invention 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- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable 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.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable 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-amino-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 the published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-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 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-1-methylpyrazole, 4,5-diamino-1- (β- hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl- 1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5- Diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4, 5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4.5 Diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4 - (ß-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, if a tautomeric equilibrium exists:

wobei:

in which:

G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a C ₁ - to C4-alkyl group, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl a (C ₁ - to C ₄₎ alkoxy (C _r to C ₄₎ alkyl group a C ₁ - to C ₄ - aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl residue, a (C ₁ - to C ₄₎ alkylamino (C _r to C ₄₎ alkyl a di - aminoalkyl (C _r to C _4), wherein the dialkyl - [(C _r to C ₄₎ alkyl] Radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) aminoalkyl, the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ - alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl radical, a s (C ₁ - to C ₄₎ alkylamino (Ci to C ₄₎ - alkyl group, a di - [(Cr to _C4) alkyl] - (C ₁ - to C ₄₎ aminoalkyl, wherein the dialkyl Radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C _4- alkyl or di- (C ₁ - 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 O 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 equals 2, n is the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

Among the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) may be mentioned in particular:

Pyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine;

3-aminopyrazolo [1,5-a] pyrimidin-7-ol;

3-aminopyrazolo [1,5-a] pyrimidin-5-ol;

2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;

2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;

2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The pyrazolo [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 coupler component.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. 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, 1-phenyl-nyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1, 3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 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 , 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-

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

Hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino- 3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-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-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-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 For example, 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, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) -amino 3,4-methylenedioxybenzene and their physiologically acceptable salts.

Particularly preferred coupler components 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.

The following coupler / developer combinations have proved particularly suitable according to the invention: 3-amino-4- (4-methoxyphenoxy) phenylamine / p-phenylenediamine 3-amino-4- (4-methoxyphenoxy) phenylamine / p-toluenediamine 3-amino-4 - (4-methoxyphenoxy) phenylamine / 2- (β-hydroxyethyl) -p-phenylenediamine 3-Amino-4- (4-methoxyphenoxy) phenylamine / N, N-bis- (β-hydroxyethyl) -p-phenylenediamine 3-Amino -4- (3-methoxyphenoxy) phenylamine / p-phenylenediamine 3-Amino-4- (3-methoxyphenoxy) phenylamine / p-toluenediamine 3-Amino-4- (3-methoxyphenoxy) phenylamine / 2- (β-hydroxyethyl) - p-phenylenediamine 3-Amino-4- (3-methoxyphenoxy) phenylamine / N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine 3-Amino-4- (2-methoxyphenoxy) phenylamine / p-phenylenediamine 3-Amino-4- (2-methoxyphenoxy) phenylamine / p-toluenediamine 3-Amino-4- (2-methoxyphenoxy) phenylamine / 2- (β- Hydroxyethyl) -p-phenylenediamine 3-Amino-4- (2-methoxyphenoxy) phenylamine / N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine

The hair colorants of the invention contain both the developer components and the coupler components preferably in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total oxidation colorant. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has been found to be useful, so a certain excess of individual oxidation dye precursors is not detrimental, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , may be included.

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

Particularly suitable precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIa),

in der unabhängig voneinander

in the independently of each other

G ₁₉ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxy-alkyl group,

G ₂₀ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

G ₂ i is hydrogen or a C 1 -C ₄ -alkyl group,

G ₂₂ is hydrogen, a C _r C ₄ alkyl group or a group -CO-G ₂₄ in which G ₂₄ is a C 1 -C ₄ alkyl group, and - G ₂₃ is one of the groups mentioned under G ₂₂ , and physiologically acceptable 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.

Particularly noteworthy 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 5, 6-Dihydroxyindolin.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIb),

in the independently of each other

G _2S is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

G ₂₆ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

G ₂₇ is hydrogen or a C 1 -C 4 -alkyl group,

G ₂₈ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-G ₃₀ , in which G ₃₀ is a C 1 -C ₄ -alkyl group, and

G ₂₉ is one of the groups mentioned under G ₂₈ , as well as physiologically acceptable 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. Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically compatible salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment, it may 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, ornithine, 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 may contain one or more substantive dyes for shading. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations 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 as well as 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) 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'-carboxylic 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.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are (a) cationic triphenylmethane dyes such as Basic Blue 7,

Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic

Blue 99, Basic Brown 16 and Basic Brown 17, as well

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, which is explicitly referred to at this point, are claimed in claims 6 to 11.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

Cl ^"

(DZ3)

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 substantive dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

The agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing 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 tinting compositions according to the invention, reference is 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 series "Dermatology" (ed. Ch. Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of Cosmetic Raw Materials", published by the European Community, available in floppy form from the Federal Association of German Industrial and Trade Companies for Medicinal Products, Reformwaren und Körperpflegemittel eV, Mannheim, incorporated by reference.

The colorants of the invention may further contain all known for such preparations active ingredients, additives and excipients. In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved 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 surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 C-men men. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanol ammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (Soap),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16, acylsarcosides having 10 to 18 C Atoms in the acyl group, acyltaurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefinsulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in the R is a preferably linear alkyl group with 10 bis 18 C-atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354, Sulfonates of unsaturated fatty acids having 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 which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 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.

Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and on

Alkylphenols having 8 to 15 C atoms in the alkyl group,

C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol

Ethylene oxide with glycerine,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. 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 one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting 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 particular work-up of these compounds. And Cio-alkyl groups essentially of C ₁₂ - - and C ₁₄ alkyl groups, mainly of C ₈ - to C ₆ -alkyl or substantially of C ₁₂ alkyl polyglycosides are those in which R ¹ consists essentially of C ₈ are particularly preferred - to C ^ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks 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 from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

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

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry 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 group. N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the coco acylaminoethylhydroxyethylcarboxymethylglycinate A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine. Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which make it possible to form internal salts are. 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 having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _12- iβ- sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.

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

Esterquats 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 marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

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 Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), 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 used as surfactant with alkyl groups may 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 having different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Furthermore, the colorants of the invention may contain other active ingredients, auxiliaries and additives, such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers , Acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylamino-ethylmethacrylate-vinyl pyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.

Butylaminoethyl methacrylate, hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobornyl acrylate 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.

For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and

Wheat protein hydrolysates, their condensation products with fatty acids and quaternized

protein,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber structure-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl -2-alkylimidazolinium methosulfate

Defoamers like silicones,

Dyes for staining 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 conventional acids, in particular

Pleasure acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ ,

C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, Spruce Needle, Horse Chestnut, Sandalwood, Juniper, Coconut, Mango, Apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosemary, Birch, Mallow, Meadowfoam, Quendel, Yarrow, Thyme, Melissa, Hominy, Coltsfoot, Marshmallow, Meristem, ginseng and ginger root ,. Cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, swelling and penetrating agents such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate, pigments,

Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

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 surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also conceivable to integrate the dye precursors in a powdered or tablet-shaped formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C ₄ -alkoH ₂ O, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents. The actual oxidative coloring of the fibers can be done basically with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate. According to the invention, however, the oxidation dye 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⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle 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, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

Suitable enzymes are e.g. Peroxidases that 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 aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its 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 of 6 to 12. Particularly preferred is the application of Hair dyes in a mildly alkaline environment. The application temperatures can be in a range between 15 and 40 ⁰ C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

Especially with 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 appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes is then rinsed and nachshampooniert if desired. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.

A second subject matter of the present invention is a process for coloring keratinic fibers, in which a hair colorant according to the invention is applied to the fibers and rinsed off again after a contact time.

A third aspect of the present invention is m-phenylenediamine derivatives of the formula (I)

in which

R ₁ , is a branched or unbranched C ₁ - to C ₆ -alkyl group which may optionally carry one or more hydroxyl groups,

R ₂ , R ₃ and R ₄ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -

Alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ alkoxy group, a C ₁ to C ₄ alkoxy (C ₁ to C ₄ ) alkyl group or a halogen atom.

In the context of this article of the present invention, reference is made to the above-mentioned preferred embodiments.

Particularly preferred m-phenylenediamine derivatives of the formula (I) are 3-amino-4- (4-methoxyphenoxy) -phenylamine, 3-amino-4- (3-methoxyphenoxy) -phenylamine and 3-amino-4- (2-methoxyphenoxy) -phenylamine.

Exemplary embodiments 1 Syntheses

1.1 3-Amino-4- (4-methoxyphenoxy) phenylamine

1.1.1 1- (4-Methoxyphenoxy) -2,4-dinitrobenzene

100 g of 2,4-dinitrochlorobenzene, 57 g of 4-methoxyphenol and 69 g of potassium carbonate were dissolved or suspended in 500 ml of dimethylformamide, and the mixture was heated to 100 ^° C. with stirring for 2 hours. The mixture was then added to 300 ml of ice, the precipitated substance was filtered off and washed with water. A sample was dried in vacuo. Melting point: 99 to 103 ⁰ C

1.1.2 3-Amino-4- (4-methoxyphenoxy) phenylamine

123 g of 1- (4-methoxyphenoxy) -2,4-dinitrobenzene (wet) were suspended in 1.8 l of ethanol + 200 ml of water, admixed with 2 g of Pd / C, 5%, and the reaction at room temperature overnight hydrogenated at 25 bar. The batch was filtered from the catalyst and concentrated to dryness.

1.2 3-Amino-4- (3-methoxyphenoxy) phenylamine

1.2.1 1-(3-Methoxyphenoxy)-2,4-dinitrobenzol

1.2.1 1- (3-Methoxyphenoxy) -2,4-dinitrobenzene

100 g of 2,4-dinitrochlorobenzene, 57 g of 3-methoxyphenol and 69 g of potassium carbonate were dissolved or suspended in 500 ml of dimethylformamide, and the mixture was heated to 100 ° C. with stirring for 2 h. The mixture was then added to 300 ml of ice, the precipitated substance was filtered off and washed with water. A sample was dried in vacuo. Melting point: 80-83 ^° C.

1.2.2 3-Amino-4- (3-methoxyphenoxy) phenylamine

130 g of 1- (3-methoxyphenoxy) -2,4-dinitrobenzene (moist) were suspended in 0.9 l of ethanol + 100 ml of water, the batch was admixed with 2 g of Pd / C, 5% strength and added at room temperature overnight Hydrogenated at 25 bar. The batch was filtered from the catalyst and concentrated to dryness.

1.3 3-Amino-4- (2-methoxyphenoxy) phenylamine

1.3.1 1 - (2-Methoxyphenoxy) -2,4-dinitrobenzene

100 g of 2,4-dinitrochlorobenzene, 57 g of 2-methoxyphenol and 69 g of potassium carbonate were dissolved or suspended in 500 ml of dimethylformamide, and the mixture was heated to 100 ° C. with stirring for 2 h. The mixture was then added to 300 ml of ice, the precipitated substance was filtered off and washed with water. A sample was dried in vacuo. Melting point: 87 to 89 ⁰ C.

1.3.2 3-Amino-4- (2-methoxyphenoxy) phenylamine

135 g of 1- (2-methoxyphenoxy) -2,4-dinitrobenzene (moist) were suspended in 1.8 l of ethanol + 200 ml of water, the batch was admixed with 2 g of Pd / C, 5% strength and added at room temperature overnight Hydrogenated at 25 bar. The batch was filtered from the catalyst and concentrated to dryness. The resulting solid residue was recrystallized from 600 ml of ethanol.

Yield: 47 g

Melting point: 93 to 95 ⁰ C. 2 colorations

2.1 Experimental procedure

For the preparation of the staining cream 50g of a cream base were weighed in a 250ml beaker and melted at 8O ⁰ C. The cream base used had the following

Composition:

Hydrenol ^® D ¹ 17.0 wt .-%

Lorol® ^® tech. ² 4.0% by weight

Texapon ^® NSO ³ 40.0% wt .-

Dehyton ^® K ⁴ 25.0 wt .-%

Eumulgin ^® B2 ⁵ 1, 5 wt .-%

Water 12.5% by weight

¹ C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² C ₁₂ .i ₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis)

³ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

⁴ N, N-Dimethyl-N- (C ₈ -i _8- cocoamidopropyl) ammonium acetobetaine (about 30% active ingredient, 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 were suspended separately in distilled water or dissolved by heating. Then ammonia (<1 ml, 25% ammonia solution) was added until the pH was between 9 and 10.

The dissolved dye precursors were incorporated successively into the hot cream. It was then made up to 97 g with distilled water and adjusted to a pH of 9.5 with ammonia. After filling with distilled water to 100 g, the mixture was stirred cold (<3O ⁰ C), resulting in a homogeneous cream. For the dyeings, in each case 25 g of dyeing cream were mixed with 25 g of the following oxidizing agent preparation.

Dipicolinic acid 0.1% by weight

Sodium pyrophosphate 0.03% by weight

Turpinal SL ^{® 6} 1, 50 wt .-%

Texapon ^® N28 ⁷ 2.00% wt .-

Acrysol ^® 22 ⁸ 0.60 wt .-%

Hydrogen peroxide, 50% 12.00% by weight

Sodium hydroxide, 45% 0.80% by weight

Water ad 100% by weight

⁶ 1-Hydroxyethane-1, 1-diphosphonic acid (about 58 - 61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

⁷ lauryl ether sulfate sodium salt (at least 26.5% active ingredient content, INCI name: Sodium Laureth Sulfate) (Cognis)

⁸ acrylic polymer (about 29.5 - 30.5% solids in water, INCI name: Acrylates / Steareth-20 Methacrylate Copolyme)

One strand of hair (80% gray, 330 mg to 370 mg heavy) was added to each of the mixtures thus obtained. Subsequently, the mixtures and the hair strands were placed on a watch glass and the hair strands well embedded in the dyeing creams. After 30 minutes (± 1 minute) Reaction time at room temperature were removed and the strands of hair so washed many times, until the color was removed with an excess of an aqueous solution Texapon ^® EVR. ⁹ The strands of hair were air-dried and their color under the daylight lamp (color tester HE240A) determined and noted (Taschenlexikon the colors, A. Kornerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag, Zurich, Göttingen).

⁹ Lauryl ether sulfate sodium salt with special additives (about 34 to 37% active ingredient content, INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis) The results obtained in the staining tests are shown in the tables below.

2.2 Coloring with 3-amino-4- (4-methoxyDhenoxv) phenvlamin

Developer component coloration p-toluenediamine sulfate black-blue

2,4,5,6-tetraaminopyrimidine sulphate dark green p-aminophenol dark brown

4,5-Dimanio-1- (2-hydroxyethyl) pyrazole sulfate dark magenta

2- (2,5-diaminophenyl) ethanol sulfate dark blue

4-amino-3-methylphenol cafe-au-lait

4-amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol dihydrochloride dark brown

N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate dark blue

2.3 Coloring with 3-amino-4- (3-methoxyphenoxv) phenγlamine

Developer component coloration p-toluenediamine sulfate black-blue

2,4,5,6-tetraaminopyrimidine sulfate deep green p-aminophenol fawn

4,5-Dimanio-1- (2-hydroxyethyl) pyrazole sulfate dark magenta

2- (2,5-diaminophenyl) ethanol sulfate black-blue

4-amino-3-methylphenol cafe-au-lait

4-Amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol dihydrochloride brown

N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate dark blue

2.4 Coloring with 3-amino-4- (2-methoxy-dhenoxv) -henivamine

Developer component coloration p-toluenediamine sulfate black-blue

2,4,5,6-tetraaminopyrimidine sulfate dark green p-aminophenol reddish brown

4,5-Dimanio-1- (2-hydroxyethyl) pyrazole sulfate dark magenta

2- (2,5-diaminophenyl) ethanol sulfate black-blue

4-amino-3-methylphenol brown

4-Amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol dihydrochloride, fawn

N, N-bis (2-hydroxyethyl) -p-phenylenediamine sulfate dark blue

Claims

P a n t a n s p r e c h e 1. An agent for coloring keratinic fibers, in particular human hair, comprising in a cosmetically acceptable carrier as coupler component at least one m-phenylenediamine derivative of the formula (I)

in which R ₁ , is a branched or unbranched C ₁ - to C ₆ -alkyl group which may optionally carry one or more hydroxyl groups, R ₂ , R ₃ and R ₄ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ - Alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ Polyhydroxyalkyl, a C ₁ - to C ₄ alkoxy, a C ₁ - to C ₄ -Aikoxy- (C ₁ - bis C ₄ ) alkyl group or a halogen atom. Composition according to Claim 1, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which the substituent R ₁ stands for a branched or unbranched C ₁ - to C ₄ -alkyl group or a branched or unbranched C ₁ - to C ₄ - monohydroxyalkyl group. 3. Composition according to claim 2, characterized in that it contains an m-phenylenediamine derivative of the formula (I), wherein the substituent R _{1 is} a methyl group or a hydroxyethyl group. Agent according to one of claims 1 to 3, characterized in that the substituent R _{2 is} hydrogen. Agent according to one of claims 1 to 4, characterized in that the substituent R _{3 is} hydrogen. 6. Composition according to one of claims 1 to 5, characterized in that the substituent R _{4 is} hydrogen. 7. Composition according to one of claims 1 to 6, characterized in that it comprises at least one m-phenylenediamine derivative selected from 3-amino-4- (4-methoxyphenoxy) phenylamine, 3-amino-4- (3-methoxyphenoxy) phenylamine and 3-amino-4- (2-methoxyphenoxy) phenylamine. 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. Composition 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 keratinous fibers, wherein an agent according to any one of claims 1 to 11 is applied to the fibers and rinsed again after a contact time. 13. m-phenylenediamine derivatives of the formula (I)

in which R ₁ , is a branched or unbranched C ₁ - to C ₆ -alkyl group which may optionally carry one or more hydroxyl groups, R ₂ , R ₃ and R ₄ independently of one another represent a hydrogen atom, a Cr to C ₄ - Alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ Polyhydroxyalkyl group, a C ₁ to C ₄ alkoxy group, a C ₁ to C ₄ alkoxy (C ₁ to C ₄ ) alkyl group or a halogen atom. 14. 3-Amino-4- (4-methoxyphenoxy) phenylamine. 15. 3-Amino-4- (3-methoxyphenoxy) phenylamine. 16. 3-Amino-4- (2-methoxyphenoxy) -phenylamine.