WO2006050768A1 - Novel m-phenylenediamine coupler compounds - Google Patents

Abstract

The invention relates to agents for colouring keratin fibres, in particular human hair, said agents containing at least one m-phenylenediamine derivative of formula (I) in a cosmetically acceptable medium as the coupler component. In said formula, R1 represents a C1-C2 alkyl group or a C1-C2 monohydroxyalkyl group, R2, R3 and R4 represent independently of one another a hydrogen atom, a methyl or ethyl group and R5 and R6 represent independently of one another a branched or unbranched C2-C3 hydroxyalkyl group. The inventive coupler components permit a coloration that produces intense colours and good to excellent fastness characteristics in the red and violet colour spectra, in particular by means of p-toluylenediamine, 4-aminophenol, 4-amino-3-methylphenol, 4,5-diamino-1-(2-hydroxyethyl)pyrazole, 1-(2-hydroxyethyl)-2,5-diaminobenzole, 2,4,5,6-tetraaminopyrimidine and bis-(2-hydroxy-5-aminophenyl)methane.

Description

 NEW M-PHENYLENDIAMIC COUPLER

The present invention relates to agents for coloring keratinic fibers containing specific m-phenylenediamine derivatives, a process for dyeing hair with these agents, and the m-phenylenediamine derivatives 3,5-bis - [(2-hydroxyethyl) amino] -anisole.

For the dyeing of keratin fibers, in particular human hair, the so-called oxidation colorants play a preferential 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.

As developer components are usually primary aromatic amines with another, 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 used.

Specific representatives are for example p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetra-aminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) - p-phenylenediarnine, 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-thiaminopyrimidine, 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.

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, 1,5,7,7,7,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1 -Phenyl-3-methyl-pyrazolone-5,2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diamino) phenoxy) -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 fulfill the following requirements: In the oxidative coupling, they must form the desired color shades in sufficient intensity and authenticity. 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, e.g. Perm 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.

With a developer component or a specific coupler / developer combination alone, it is generally not possible to obtain a color shade which acts naturally 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 special m-phenylenediamine derivatives satisfy the requirements imposed on coupler components to a high degree. The coupler components according to the invention in particular with p-toluenediamine, 4-aminophenol, 4-amino-3-methylphenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 1- (2-hydroxyethyl) -2,5-diaminobenzene , 2,4,5,6-tetraaminopyrimidine and bis (2-hydroxy-5-aminophenyl) methane dyeings with high color intensities and good to very good fastness properties in the red and violet 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)

where R ¹ is a C ₁ to C ₂ alkyl group or a C ₁ to C ₂ monohydroxyalkyl group,

R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a methyl or an ethyl group,

R ⁵ and R ⁶ independently of one another represent a branched or unbranched C ₂ - to C ₆ -

Hydroxyalkyl.

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 no obstacle to 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, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.

Some structurally related m-phenylenediamine derivatives are already known from the prior art as coupler components. International Patent Publication WO-A2-93 / 10 744 discloses a method for dyeing hair in an acidic medium (pH <7) using structurally related m-phenylenediamine derivatives. Specifically, there is the compound 2,4-di- (ß-hydroxyethylamino) -1-methoxybenzo! described. The compounds now claimed differ from this Compound in that they are structural isomers. This document gives no indication of the compounds now claimed and their excellent dyeing properties. The m-phenylenediamine derivatives according to the invention which are present in the colorant are distinguished, in particular, by the fact that intensive, attractive reddish violet shades can be obtained with a number of standard developers, while the coupler component known from WO-A2-93 / 10 744, in combination with corresponding standard developers, is generally blue Color tones results.

Also in WO 2004/058205 A1, structurally related m-phenylenediamine derivatives are described as coupler components in colorants for coloring keratinic fibers. The aromatic nucleus carries, in addition to the amino substituents, an alkoxy group which may be located in the o- or m-position relative to the two amino groups. The examples describe m-phenylenediamine derivatives whose alkoxy group is in the ortho position to the two amino groups. m-phenylenediamine derivatives having an alkoxy group located in the m-position to the two amino groups are generally described, but concrete compounds having such a substitution pattern are not mentioned.

The keratinic fiber coloring agents according to the invention preferably contain at least one m-phenylenediamine derivative of the formula (I) in which R ⁵ and R ^{6 are} identical substituents, more preferably a 2-hydroxyethyl group or a 3-hydroxypropyl group. Particularly preferably, the substituents R ⁵ and R ⁶ each represent a 2-hydroxyethyl group.

Furthermore, according to the invention, the m-phenylenediamine derivatives of the formula (I) are preferred in which the substituent R ^{1 is} a methyl group.

Furthermore, according to the invention, the m-phenylenediamine derivatives of the formula (I) are preferred in which R ² , R ³ and R ^{4 are} each independently of one another hydrogen or a methyl group. Particularly preferably, R ² , R ³ and R ^{4 are} hydrogen.

The agent according to the invention particularly preferably contains the m-phenylenediamine derivative 3,5-bis - [(2-hydroxyethyl) amino] -anisole.

The m-phenylenediamine derivatives of the formula (I) can be prepared by means of conventional organic methods. For example, reference is made at this point to the experimental procedures in the context of the embodiments. In addition to the m-phenylenediamine derivatives of the formula (I), the colorants according to the invention may furthermore contain at least one developer component.

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

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 d- 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 group a 4'-aminophenyl, or C ₁ - to C ₄ alkyl radical substituted with a nitrogenous group, a phenyl group or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C _r to C ₄ -mono-hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C 1 -alkyl ₎ - C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to 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 C ₁ - to C ₄ alkyl radical, a C ₁ - to C ₄ -Monohydroxyalkylrest, a C ₂ - to C ₄ polyhydroxyalkyl, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ - to C ₄ - acetylaminoalkoxy, C ₁ - to C ₄ - mesylaminoalkoxy or 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 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. According to the invention, preferred C 1 to C ₄ alkoxy radicals 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, in particular, the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -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 (.beta.-hydroxyethyl) amino-2-chloroaniline, 2- (.beta.-hydroxyethyl) -p-phenylenediamine, 2- (.alpha., .Beta.

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-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo -1, 4-dioxane and their physiologically acceptable salts.

According to the invention particularly preferred p-phenylenediamine ^derivatives' of the formula (E1) are p-phenylenediamine, p-toluylenediamine, 2- (beta-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-phenylenediamine and N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine. According to the invention, it may further be preferred to use as the 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:

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, of one or more nitrogen-containing groups and / or one or more heteroatoms such Oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C _r to C ₈ alkoxy, 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 -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridge Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred binuclear developer component of the formula (E2) are in particular: N ₁ N'-bis (.beta.-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 (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl- N, N'-bis (4'-arnino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) -propane -2-ol, 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 their physiologically acceptable salts.

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-tetraoxadecan or one of its physiologically acceptable salts.

Bis (2-hydroxy-5-aminophenyl) methane is a most preferred dinuclear developing agent of formula (E2).

Furthermore, it may be preferred according to the invention to use as the developer component a p-amino phenol 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 ) - AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, a hydroxy (C _r to C ₄ ) - alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl- (C ₁ -C ₄ ) -aminoalkyl radical or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ -C ₄ ) -alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a d- to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ - -alkoxy - (C ₁ - to C ₄₎ alkyl group a C ₁ - to C ₄ -aminoalkyl radical or a Ci to _C4 - cyanoalkyl,

G ¹⁵ is hydrogen, 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 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, A-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.

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 A-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. Furthermore, the developer component may 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-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 Laid-Open Specification 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 Triamino pyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

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

in which:

G, G, G and G are independently a Wasserst off 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 a (C ₁ - to C ₄₎ alkoxy (Cr to _C4) 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 -, alkyl to C ₄₎ alkylamino (Cr to _C4) a DH (C ₁ - to C ₄₎ alkyl] - (C _r to C ₄ aminoalkyl), wherein the dialkyl residues optionally a Carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (Cr to C ₄ ) - [hydroxyalkyl] - (Cr to C ₄ ) -aminoalkyl radical which are X radicals off independently a Wasserst atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C _r -C ₄ hydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ - Aminoalkyl radical, a (C ₁ - to C ₄ Alkyl to C _4), a Di -) - alkylamino (C ₁ to C ₄ aminoalkyl), wherein the dialkyl residues optionally a carbon cycle or a - [(C _r to C ₄₎ alkyl] - (C ₁ heterocycle form with 5 or 6 chain links, a C ₁ - to C ₄ hydroxyalkyl or a di- (C ₁ - to C ₄ hydroxyalkyl) aminoalkyl group, an amino group, a C ₁ - to C ₄ -AiKyI- 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 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 when p + q equals 2, n has 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. If the pyrazolo [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 represented, for example, in the following scheme:

Among the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) can be called 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 from an aminopyrazole or from hydrazine.

In a further preferred embodiment, the dyeing agents according to the invention contain at least one further coupler component. Examples of further coupler components which can be used are m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives. 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1-naphthol, 1-naphthol, 1-naphthol, 1-naphthol are particularly suitable. Phenyl-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-methyl-sorcinol and 2-methyl-4-chloro-5-aminophenol.

Further 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-methyl phenol, 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 2,4-diaminophenoxyethanol,

1, 3-bis- (2 ', 4'-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hydroxyethyl-amino) -benzene, 1, 3-bis- (2', 4 ' -diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene 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, for example, 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, for example, 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 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred further 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:

3,5-bis - [(2-hydroxyethyl) amino] -anisole / p-toluenediamine,

3,5-bis - [(2-hydroxyethyl) amino] -anisole / 4-aminophenol,

3,5-bis - [(2-hydroxyethyl) amino] -aniso! / 4-amino-3-methylphenol,

3,5-bis - [(2-hydroxyethyl) amino] -anisole / 4,5-diamino-1- (2-hydroxyethyl) pyrazole,

3,5-bis - [(2-hydroxyethyl) amino] -anisole / 1- (2-hydroxyethyl-2,5-diaminobenzene, 3,5-bis - [(2-hydroxyethyl) amino] -anisole / bis- (2-hydroxy-5-aminophenyl) methane as well

3,5-bis - [(2-hydroxyethyl) amino] -anisole / 2,4,5,6-tetraaminopyrimidine.

The hair colorants according to 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 .-%, in each case 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 proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components are 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 it is preferred to use those indoles and indolines which have at least one hydroxyl 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 further 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 the independently of each other

A ¹ is hydrogen, a C _r C ₄ -alkyl group or a C _r C ₄ -hydroxy-alkyl group,

- A ² is hydrogen or a -COOH group, wherein the -COOH group also as

May be salt with a physiologically acceptable cation,

A ³ is hydrogen or a C 1 -C ₄ -alkyl group, and

- A ⁴ and A ⁵ are each independently hydrogen, a C _r C ₄ alkyl group or a group -CO-A ⁶ , in which A ⁶ is a C _r C ₄ alkyl group, as well as physiologically acceptable salts of these compounds an organic or inorganic acid.

Preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxy-indoline, 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),

where the radicals A ¹ , A ² , A ³ , A ⁴ and A ^{5 have} the meanings given above, and physiologically tolerable salts of these compounds with an organic or inorganic acid.

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 acceptable salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used. The indole or Indoün derivatives are contained in these 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 shade. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those under 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-tetrahydroch inoxaline, 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 as

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

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

CH ₃ SO ₄ ^'

Cf

(DZ5)

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 driven ver¬ 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 inventive hair dye, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. Toxi¬ ecological, 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" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", Issued by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

The colorants according to the invention may furthermore contain all active ingredients, additives and auxiliaries known for such preparations. In many cases, the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has 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. Legs Carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. 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 so¬ as the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C-atoms in the Alkanolgrup- Pe, linear fatty acids with 10 bis 22 carbon atoms (soaps),

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 = O 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 = O or 1 to 12,

Blends 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 1 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 alkylphenols having 8 to 15 carbon atoms in the alkyl group, C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ -Alkylmono- and -oligoglycoside and their ethoxylated analogs and addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated Ri¬ zinusöl.

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

The alkyl radical R 'contains from 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl branched in 2-Ste! Ment 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 so-called "oxo-alcohols" are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R '. Usually, however, these compounds are produced 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.

Particular preference is given to those alkylpolyglycosides in which R 'consists essentially of C ₈ and C ₁₀ -alkyl groups, essentially of C ₁₂ and C ₁₄ -alkyl groups, essentially of C ₈ - to C- ₆ alkyl groups or consisting essentially of C ₁₂ - to C ₁₆ 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 Used oligosaccharides. 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 particularly preferred are 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 a perfume oil on the hair going beyond 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 those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^H or -SO ₃ ^H group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyl- dimethylammonium glycinate, and 2-alkyl-3-carboxamethyl-3-hydroxyethylimidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. 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 to be understood as meaning those surface-active compounds which, in addition to 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 for the formation of internal Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkyl Propionic 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, acylaminoethylaminopropionat the coconut and the C _{12-i 8} acyl sarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. As cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, Lauryldimethylbenzylammoniumchlorid and Tricetylmethylam- moniumchlorid, as well as under the INCI names Quaternium-27 and Quaternium-83 known Imidazoiium compounds. 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 structural element. Preferred esterquats 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-Palmitoyloxy- ethyl) dimethyl ammonium 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 trimethyl isilylamodimethicone), Dow Corning 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 (Her¬ manufacturers: Th. Goldschmidt; diquaternary Poiydimethylsiloxane, 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 plant 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 which are obtained as catalysts in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alkoxides. Limited homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or -aikoholates are used as catalysts. The use of products with narrow homolog distribution is preferred.

Furthermore, the colorants according to the invention may contain further active ingredients, auxiliaries and additives, for example nonionic polymers such as vinylpyrrolidone / inylacrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / inylacetate 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-ethylmethane acrylate-vinylpyrrolidone 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. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as e.g. Bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example 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 hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 -alkylimidazolinium methosulfate defoamers such as silicones, dyes for staining the agent,

Antidandruff active ingredients 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, for example, customary acids, especially edible acids and bases, active substances 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, quenelle, yarrow, thyme, melissa, toadstool, 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,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,

Hydrogencarbonates, guanidines, ureas as well as 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

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

- Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants containing.

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, 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 3 to 70% by weight of a C ₁ -C ₄ -alkoxy, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example 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 storage products of urea, melamine and sodium borate. According to the invention, however, the dyeing center! may also be applied to the hair together with a catalyst which inhibits the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . 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, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, 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 from 6 to 12. Unless explicitly stated otherwise, the pH values given in this specification are the pH values at 25 ^° C. The use of the hair dyeing agent in a weakly alkaline medium is particularly preferred. The application temperatures can be in a range between 15 and 40 ⁰ C. After an eggπwirkungszeit of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The Nach¬ wash with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

In particular, with hair that is difficult to dye, the preparation with the dye precursors may 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 Peroxidisulfat- solutions may be preferred as the oxidizing agent.

A second subject matter of the present application is the use of the inventive m-phenylenediamine derivatives for dyeing keratinic fibers. A third object 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 fourth subject of the present invention is the m-phenylenediamine derivative 3,5-bis [(2-hydroxyethyl) amino] -anisole.

The invention furthermore relates to the first intermediate of the synthesis of the inventive m-phenylenediamine, 2-chloroethyl-3 - {[(2-chloroethoxy) carbonyl] amino} -5-methoxyphenylcarbamate.

The invention additionally relates to the second intermediate of the synthesis of the inventive m-phenylenediamine, 3- [3-methoxy-5- (2-oxo-1,3-oxazolidin-3-yl) phenyl] - 1, 3 oxazolidin-2-one.

The invention will be further elucidated on the basis of the following examples, wherein the examples are intended to facilitate the understanding of the principle according to the invention and are not to be understood as limiting the general subject matter of the invention.

embodiments

1 syntheses

1.1 3,5-bis - [(2-hydroxyethyl) amino] -anisole

1.1.1 3,5-Diaminoanisole

30 g of 3,5-Dinitroanisoi were dissolved in 360 ml of ethanol and 40 ml of water, treated with 0.3 g of Pd / C (5%) and then hydrogenated at room temperature for 6 hours at atmospheric pressure. After hydrogenation, the catalyst was filtered off and the filtrate was concentrated to dryness on a rotary evaporator. Yield: 17.6 g (85%)

Melting point: 80 - 82 ⁰ C

1.1.2 2-Chloroethyl-3 - {[(2-chloroethoxy) carbonyl] amino} -5-methoxyphenylcarbamate

62 g of 3,5-diaminoanisole and 145 g of calcium carbonate were placed in 0.5 l of dioxane and heated to 90 ⁰ C. Within 15 minutes, 168 g of 2-chloroethyl chloroformate were added and stirring was continued for 4 hours at this temperature. After allowing to cool, and the mineral salts were filtered off. The filtrate was poured into ice-water, the product formed was filtered off and dried in vacuo. Yield: 106 g (67%)

Melting point: 159 to 164 ⁰ C

1.1.3 3- [3-Methoxy-5- (2-oxo-1,3-oxazolidin-3-yl) phenyl] -1,3-oxazolidin-2-one

400 ml of sodium hydroxide solution (20%) were initially charged and heated to 45 ⁰ C. Subsequently, 106 g of bis (2-chloroethyl) (5-methoxy-1, 3-phenylene) biscarbamate were added in portions, and stirred at 45 ⁰ C for a further 4 h. Subsequently, the batch was poured onto ice and neutralized with hydrochloric acid. The precipitated product was filtered off and dried overnight in vacuo. Yield: 96 g (87%)

Melting point: 199-200 ° C 1.1.4 3,5-Bis - [(2-hydroxyethyl) amino] -aniso!

400 ml of 20% NaOH and 400 ml of dioxane were initially charged, heated to reflux and then in portions with 96 g of 3,3 '- (5-methoxy-1, 3-phenylene) bis (1, 3-oxazolidin-2-one ). After the addition, the reaction mixture was heated for a further 8 h under reflux. The mixture was allowed to cool to room temperature overnight and the reaction mixture was added to 1.5 L of ice-water. The mixture was then neutralized with hydrochloric acid, the aqueous phase saturated with NaCl and extracted several times with ethyl acetate. The combined organic phases were concentrated on a rotary evaporator to dryness. Yield: 71 g (90%)

2 colorations

2.1 Experimental procedure

For the preparation of the dyeing cream 50 g of a cream base were weighed into a 250ml glass Becher¬ 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 Ci ₆ -i ₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² C _12-18 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 _8-18 -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 (<30 ⁰ C), resulting in a homogeneous cream.

For the dyeings, 25 g of dyeing cream were mixed with 25 g of the following oxidizing agent preparation (unless stated otherwise). 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 aqueous excess Texapon EVR ^® solution. ⁹ The strands of hair were air-dried and their color was determined and recorded under the daylight lamp (color tester HE240A) (Taschenlexikon der Farben, A. Komerup 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 ₁ Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis)

The results obtained in the staining tests are shown in the table below. 2.2 colorations with 3,5-bis - [(2-hydroxyethyl) amino] -anisole

2.3 colorations with 2,4-bis - [(2-hydroxyethyl) amino] -anisole

For comparison, dyeing tests were carried out using the structurally related compound 2,4-bis - [(2-hydroxyethyl) amino] -anisole to be used according to the invention. The results obtained are shown in the table below.

It is found that when 2,4-bis - [(2-hydroxyethyl) amino] -anisole is used, blues are generally obtained, while the use of the coupler components to be used according to the invention gives the desired red-violet tones.

Claims

Patent claims

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)

wherein R ¹ is a C ₁ to C ₂ alkyl group or a C ₁ to C ₂ monohydroxyalkyl group,

R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a methyl or an ethyl group, and

R ⁵ and R ⁶ independently of one another represent a branched or unbranched C ₂ - to C ₃ -hydroxyalkyl group.

2. Composition according to claim 1, characterized in that it contains an m-phenylenediamine derivative of the formula (I), wherein R ⁵ and R ^{6 are} identical substituents.

3. Composition according to one of claims 1 or 2, characterized in that it contains an m-phenylenediamine derivative of the formula (I), in which R ⁵ and R ^{6 are} a 2-hydroxyethyl group.

4. Composition according to one of claims 1 to 3, characterized in that it contains an m-phenylenediamine derivative of the formula (I), wherein R ^{1 is} a methyl group.

5. Composition according to one of claims 1 to 4, characterized in that it contains an m-phenylenediamine derivative of the formula (I), in which R ² , R ³ and R ^{4 are} each hydrogen.

6. Composition according to one of claims 1 to 5, characterized in that it is the m-phenylenediamine derivative 3, 5-bis - [(2-hydroxyethyl) amino] -aniso! contains.

7. Composition according to one of claims 1 to 6, characterized in that it contains at least one developer component.

8. Composition according to one of claims 1 to 6, characterized in that it contains at least one further coupler component.

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

10. A process for dyeing keratinous fibers, wherein an agent according to any one of claims 1 to 9 applied to the fibers and rinsed again after a contact time.

1, 3,5-Bis - [(2-hydroxyethyl) amino] -anisole.