EP1353640A1

EP1353640A1 - Novel coupling components for oxidative dyes

Info

Publication number: EP1353640A1
Application number: EP02715451A
Authority: EP
Inventors: David Rose; Horst Höffkes; Bernd Meinigke
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-01-27
Filing date: 2002-01-18
Publication date: 2003-10-22
Also published as: DE10103657A1; WO2002058652A1

Abstract

The invention relates to 1,2,3,4 tetrahydroquinoline derivatives of formula (I), where R1 = H, a C¿1?-C4 alkyl group, a C1-C4 perfluoroalkyl group, a C2-C4 monohydroxyalkyl group, a C2-C5 polyhydroxyalkyl group, a C2-C4 alkenyl group, a C2-C4 aminoalkyl group, a benzyl group, a piperidinoalkyl group or a morpholinoalkyl group; R?2, R3, R4 and R5¿ independently = H, or a C¿1?-C4 alkyl or perfluoroalkyl group; R?6 and R8¿ independently = H, halogen, a C¿1?-C4 alkoxy group, a C1-C4 alkoxy group, a C1-C4 alkyl or perfluoroalkyl group, a C2-C4 monohydroxyalkyl group or a C1-C5 polyhydroxyalkyl group; R?7¿ = H, halogen or a C¿1?-C4 alkoxy group, A = a hydroxy group, a NR?9R10¿ group, where R?9 and R10¿ independently = H, a C¿1?-C4 alkyl group or a C2-C4 monohydroxyalkyl group. Said 1,2,3,4 tetrahydroquinoline derivatives and the physiologically acceptable salts thereof are suitable as coupling components for the production of oxidative dyes, containing conventional developing or coupling compounds in a carrier suitable for dyeing. On dyeing, for example, human hair, a colour tone in the red to blue region which is fast to intensive light and washing is obtained.

Description

"New Coupler Component for Oxidation Colorants"

The invention relates to agents for dyeing keratin fibers which contain special derivatives of 1,2,3,4-tetrahydroquinoline as a coupler component in combination with at least one developer component, a process for dyeing keratin fibers with these agents and the use of 1,2,3 , 4-tetrahydroquinoline derivatives as a coupler component in oxidation colorants for coloring keratin fibers.

Keratin fibers are understood according to the invention to mean furs, wool, feathers and in particular human hair. Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with colorants, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally sensitive to shampooing, so that a frequently undesirable shift in shades or even a visible "discoloration" can occur.

The so-called oxidation dyes play a special role in dyeing keratin fibers, especially hair, because of their intense colors and good fastness properties, which are achieved at a relatively low dyeing temperature and in short dyeing times. Such colorants contain a developer component in a suitable, usually aqueous carrier, which, under the influence of atmospheric oxygen or Oxidizing agents form the dye by oxidative coupling. This dye can be intensified by coupling with another developer component or with so-called coupler components, which cannot form any dyes themselves, and the shade can be modified.

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

For hair dyes and tints, the color shades in the red and brown areas are of particular importance, since they are absolutely necessary to produce natural-looking hair colors. Oxidation colorants in the red and brown areas, such as those e.g. with the combination of 2,4,5,6-tetraaminopyrimidine with 2-methylresorcinol are not yet optimal with regard to the uniformity of the color coating. Direct dyes are usually less washfast and therefore not so well suited for combination with oxidation dyes.

For these reasons, there is a need for new oxidation dye precursors and new combinations of dye precursors that enable the above-mentioned parameters to be improved. We have surprisingly found that certain 1,2,3,4-tetrahydroquinoline derivatives meet the above requirements in an outstanding manner, because they provide particularly intense shades in the red to blue range. Furthermore, especially with the developer component 2,4,5,6-tetraaminopyrimidine dark green nuances in the coloring of keratin fibers accessible. All color shades achieved are particularly washable and lightfast.

A first object of the invention is therefore an agent for dyeing keratin fibers, in particular human hair, which contains at least one developer component and at least one coupler component in a carrier suitable for dyeing, characterized in that it contains at least one compound of the formula I or the like as a coupler component contains appropriate physiologically compatible salt,

(I) where

R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a Cι-C ₄ perfluoroalkyl group, a C ₂ -C ₄ monohydroxyalkyl group, a C ₂ -C ₅ polyhydroxyalkyl group, a C ₂ -

C ₄ alkenyl group, a C ₂ -C aminoalkyl group, a benzyl group, a

Pipendinoalkyl group or a morpholinoalkyl group,

R ² , R ³ , R ⁴ and R ⁵ independently of one another represent hydrogen or a -C-C -

Alkyl or perfluoroalkyl group,

R ⁶ and R ⁸ independently of one another represent hydrogen, halogen, a C 1 -C ₄ -

Alkoxy group, a C 1 -C ₄ - alkyl or perfluoroalkyl group, a C 1 -C -

Monohydroxyalkyl group or a C -C ₅ polyhydroxyalkyl group,

R ⁷ represents hydrogen, halogen or a C 1 -C ₄ alkoxy group,

A stands for a hydroxy group or a -NR ⁹ R ¹⁰ group, where R ⁹ and R ¹⁰ independently of one another represent hydrogen, a C ₁ -C ₄ alkyl group, a C ₂ -C ₄ -

Monohydroxyalkyl group or a C ₂ -C ₅ polyhydroxyalkyl group. Examples of C 1 -C ₄ alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C ₂ -C ₄ alkenyl groups are vinyl, allyl and butenyl, vinyl and allyl being particularly preferred. Preferred C ₂ -C ₄ monohydroxyalkyl groups are the 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl groups; 2-Hydroxyethyl is a particularly preferred hydroxy alkyl group. Preferred C ₂ -C ₄ polyhydroxyalkyl groups are α, β-dihydroxyethyl, β, γ-dihydroxypropyl. According to the invention, fluorine, chlorine and bromine are preferred as halogen substituents. Chlorine and bromine are particularly preferred.

Physiologically acceptable salts include salts of inorganic or organic acids, e.g. B. hydrochlorides, sulfates or hydrobromides understood.

Preferred compounds of the formula I are those in which A is an NH ₂ group or a hydroxyl group.

Furthermore, compounds of the formula I are preferred in which R ^{1 represents} hydrogen, a - C ₄ alkyl group, a benzyl group, a C -C ₄ alkenyl group or a C ₂ -C ₄ monohydroxyalkyl group.

Also preferred are compounds of formula I in which R ⁶ , R ⁷ and R ^{8 represent} hydrogen, a halogen or a - -alkoxy radical. Hydrogen, chlorine, bromine, a methoxy and ethoxy radical are particularly preferred.

Such compounds of the formula I are also preferred according to the invention in which R ² , R ⁴ and R ^{5 are} hydrogen.

Particularly preferred tetrahydroquinoline derivatives of the formula I are 7-hydroxy-1,2,3,4-tetrahydroquinoline and 7-amino-l, 2,3,4-tetrahydroquinoline.

The tetrahydroquinoline derivative derivatives of the formula I, for example 7-hydroxy-l, 2,3,4-tetrahydroquinoline or 7-amino-l, 2,3,4-tetrahydroquinoline, are prepared by a method known from US Pat. No. 5,283,336 Method. The synthesis of N- Alkyl-7-amino-l, 2,3,4-tetrahydroquininaldine derivatives are known from the literature (Buchmann et al., J. Prakt. Chem. (1962), 4 vol. 16, 55.). The trivial name chinaldin means a 1,2,3,4-tetrahydro-2-methyl-quinoline. Further compounds of the formula (I) according to the invention are 7-amino-l, 2,3,4-tetrahydro-3-methyl-quinoline, 7-amino-l, 2,3,4-tetrahydro-4-methyl-quinoline , the 7-amino-l, 2,3,4-tetrahydro-l-methyl-quinoline and the 7-amino-1-ethyl-1, 2,3, 4-tetrahydroquinoline.

In addition to the tetrahydroquinoline derivative according to the invention, the agents according to the invention further contain at least one developer component. Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and their derivatives are usually used as developer components ,

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

in which

- G ¹ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, a Cι-C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (Cι-C) alkoxy (C -C _{_4!)} alkyl radical, a 4'-aminophenyl radical or a C 1 -C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical,

- G ² represents a hydrogen atom, a dC ₄ -alkyl radical, a Cj-C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a (C! -C ₄ ) alkoxy- (Cι-C ₄ ) - alkyl radical or a Cj-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 -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxy alkyl radical, a C2-C4 polyhydroxyalkyl radical, a CrC / i-hydroxyalkoxy, a CrC ₄ - acetylaminoalkoxy, a Cι-C ₄ mesylaminoalkoxy or a Cι-C ₄ - carbamoylaminoalkoxy,

- G ⁴ represents a hydrogen atom, a halogen atom or a Cj-C ₄ alkyl radical or

- If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of the C 1 -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. Preferred C 1 -C ₄ alkoxy radicals according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ -C ₄ monohydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. An example of a preferred C ₂ -C ₄ polyhydroxyalkyl group is the α, β-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of formula (II) are especially the amino groups, _Cι-C4 monoalkylamino, Cι-C ₄ dialkylamino, Cι-C ₄ - trialkylammonium, Cι-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 (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (ß-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (ß-hydroxyethyl) amino- 2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (ß-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl 1 -p-phenylene-diamine, N, N-dimethy 1-3 - methyl-p-phenylene-diamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylene-diamine, N- (ß, γ-

Dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acetylaminoethyloxy) -p- phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-l, 4-dioxane and their physiologically tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

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

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

in which: 1

- Z and Z independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a dC ₄ alkyl radical, by a C 1 -C ₄ monohydroxyalkyl radical and / or by a bridging Y or which is optionally part of a bridging ring system is

- The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or -CC ₈ alkoxy groups, or a direct bond,

- G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a Cι-C ₄ - alkyl group, a Cι-C alkyl ₄ -Monohydroxy, a C ₂ -C ₄ - polyhydroxy alkyl group, a Cι-C ₄ -aminoalkyl or a direct connection to bridge Y,

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

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

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -l, 3-diamino-propan-2-ol, N, N'-bis (ß-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) -tetra-methylenediamine, N, N ' -Bis- (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methyl-aminophenyl) tetramethylene diamine, N, N'-bis (ethyl) ) -N, N'-bis- (4'-amino-3'-methylphenyl) -ethylenediamine, bis- (2-hydroxy-5-aminophenyl) -methane, 1,4-bis- (4'-aminophenyl) - diaza-cycloheptane, 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. Very particularly preferred dinuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -l, 3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -l, 4-diazacycloheptane and l, 10-bis (2 ', 5'-diaminophenyl) - l, 4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

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

in which

- G ¹³ represents a hydrogen atom, a halogen atom, a dC alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl radical, a C ₁ -C ₄ - Aminoalkyl radical, a hydroxy (C ₁ -C ₄ ) alkylamino radical, a - hydroxy alkoxy radical, a C ₁ -C ₄ hydroxyalkyl (C ₁ -C) aminoalkyl radical or a (di-dG _t -alkylamino) - (C _! -C ₄ ) alkyl radical, and

- G ¹⁴ represents a hydrogen or halogen atom, a dC ₄ - alkyl group, a Cι-C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a _(Cι-C4) alkoxy- (Cι-C ₄₎ - alkyl radical, a -C-aminoalkyl radical or a d- C ₄ cyanoalkyl radical,

- G ¹⁵ stands for hydrogen, a dC ₄ alkyl radical, a C ₄ -C ₄ monohydroxy alkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

- G ¹⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are defined analogously to the above statements. Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2- ( (diethylamino) methyl) phenol and their physiologically tolerable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-

((diethy lamino) methyl) phenol.

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

Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts. According to the invention, pyrimidine or pyrazole derivatives are preferred.

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

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988, such as 4,5- Diamino-l-methylpyrazole, 4,5-diamino-l- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-l - (4'-chlorobenzyl) pyrazole, 4,5-diamino -l, 3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l- methyl-3-phenylpyrazole, 4-amino-l, 3-dimethyl-5-hydrazinopyrazole, l-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole , 4,5-diamino-l-tert-butyl-3-methylpyrazole, 4,5-diamino-l- (ß-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-l-methylpyrazole, 4 , 5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-l, 3-dimethylpyrazole, 3, 4 , 5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino-4 (β-hydroxyethyl) amino-1-methylpyrazole.

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- (ß-

Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

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

in which:

- G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a d- C - alkyl radical, an aryl radical, a dC monohydroxy alkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl radical a (-C-C ₄ ) alkoxy (dC ₄ ) alkyl group. a Cj-C ₄ - aminoalkyl radical, which can optionally be protected by an acetyl-ureide or sulfonyl radical, a (-C-C ₄ ) alkylamino (dC ₄ ) alkyl radical, a di - [(dC ₄ ) - alkyl] - (dC ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a d- C ₄ -monohydroxyalkyl- or a di- (-C-C ₄ ) - [hydroxyalkyl] - (C ₁ -C ₄ ) aminoalkyl radical, the X radicals are each independently a hydrogen atom, a dC ₄ - alkyl group, an aryl group, a Cι-C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl group, a Cι-C ₄ aminoalkyl radical, a (dC ₄ ) -Alkylamino- (-C-C ₄ ) - alkyl radical, a di - [(-C-C ₄ ) alkyl] - (C! -C) aminoalkyl radical, the dialkyl radicals optionally having a carbon cycle or a heterocycle with 5 or Form 6 chain links, a C ₁ -C ₄ monohydroxyalkyl or a di (C) -C ₄ - hydroxyalkyl) aminoalkyl radical, an amino radical, a C _! -C ₄ - alkyl or di (dC ₄ - hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3,

- p has the value 0 or 1, q has the value 0 or 1 and

- n has the value 0 or 1, with the proviso that

- the sum of p + q is not equal to 0,

- if p + q is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

- if p + q is 1, n is 1, and the groups NG ^I7 G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

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

Among the pyrazole [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

- pyrazole- [1,5-a] pyrimidine-3,7-diamine; 2,5-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine; Pyrazole- (1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethylpyrazole- [1,5-a] -pyrimidine-3,5-diamine;

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

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

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

2 - [(3-amino pyrazol- [l, 5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

2 - [(7-amino pyrazol- [l, 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;

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

2,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

2,5, N7, N7-tetramethylpyrazole- [1,5-a] pyrimidine-3,7-diamine; as well as their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

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

Preferred developer components are pyrimidine derivatives, pyrazole derivatives, p-aminophenol derivatives and p-diaminobenzene derivatives. Particularly preferred developer components are p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, N, N-bis- (ß-hydroxyethyl) -p-phenylenediamine, N, N'-bis- (ß- hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -l, 3-diamino-propan-2-ol, bis- (2-hydroxy-5-aminophenyl) -methane, N, N'-bis- (4'-aminophenyl) - 1, 4-diazacycloheptane, 1, 10-bis (2 ', 5'-diaminophenyl) -l, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol , 4-amino-3-fluorophenol, o-aminophenol, 4-amino-2-aminomethylphenol, 2-amino-5-methylphenol, 4-amino-2 - ((diethylamino) methyl) phenol, 2-amino-4-methylphenol , 2-amino-4-chlorophenol, 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, 2,5, 6-triaminopyrimidine, 1 - (2 '-hydroxy- 5' -aminobenzyl) - imidazolidin-2-one and 4,5-diamino-l- (2'-hydroxyethyl) pyrazole.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. According to the invention, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are used in particular as further coupler components.

Further coupler components preferred according to the invention are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 , 6-Dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2 ' -Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2, 4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 1-methoxy- 2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2 ', 4'-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -l-methylbenzene and l amino-3-bis- (2'-hydroxyethyl) aminobenzene, o-diamino benzene and its derivatives such as 3,4-diamino benzoic 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-l-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-l-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as l-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 l-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene,

Particularly preferred coupler components are 2-amino-3-hydroxypyridine, 2-amino-3-hydroxy-5-chloropyridine, 3-amino-2-methylamino-6-methoxy-pyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, m-phenylenediamine, 2,6-bis (2-hydroxyethylamino) toluene, 3-amino-2,4-dichlorophenol, 3-amino-2-chloro-6-methylphenol , 5-amino-4-chloro-2-methylphenol, 5- (ß-hydroxyethyl) amino-2-methylphenol, 5-amino-2-methylphenol, 2-methylresorcinol, 2- (2 ', 4'-diaminophenoxy) ethanol, l, 3-bis- (2 ', 4'-diamino- phenoxy) propane, resorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, m-aminophenol, 1, 7-, 2,7- and 1,5-dihydroxynaphthalene as well as 4-hydroxyindole and 6-hydroxyindole.

The hair colorants according to the invention preferably contain both the developer components and the coupler components in an amount of 0.005 to 10% by weight, preferably 0.1 to 5% by weight, in each case based on the total oxidation colorant.

Developer components and coupler components are generally used in approximately molar amounts to one another. If molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, 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 , can be included.

In a preferred embodiment, the hair colorants according to the invention contain, in addition to the oxidation dye precursors, customary direct dyes for further modification of the color shades.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) - aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1 - (2'-

Hydroxyethyl) 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 their 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 can contain a cationic direct dye. Are particularly preferred

(a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and

(c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as are mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11.

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

CH ₃ SO ₄ ^"

he

The compounds of the formulas (DZl), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^® , are particularly preferred direct dyes.

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

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

The agents according to the invention can furthermore contain precursors of nature-analogous dyes. Such indoles and. Are preferred as precursors of nature-analogous dyes Indolines are used in the agents according to the invention which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.

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

R ¹ (Ha)

in the independently of each other

R ¹ represents hydrogen, a dC ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a Ci

C ₄ monohydroxy alkyl group or a C ₂ -C ₄ alkenyl group

R ² represents hydrogen or a -COOH group, the -COOH group also as

Salt with a physiologically compatible cation can be present,

R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,

R ⁴ represents hydrogen, a dC ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a dC ₄ alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline. Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular the 5 6-Dihydroxyindolin.

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

R ¹

(IIb)

in the independently of each other

C ₄ monohydroxyalkyl group or a C ₂ -C ₄ alkenyl group,

R ² represents hydrogen or a -COOH group, the -COOH group also as

Salt with a physiologically compatible cation can be present,

R ³ represents hydrogen or a -CC alkyl group,

R ⁴ represents hydrogen, a dC ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a dC ₄ alkyl group, and

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Within this group, particular mention should be made of N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 -Dihydroxyindol.

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

In particular when using dye precursors of the indoline or indole type, it has proven to be advantageous to use an amino acid and / or an oligopeptide as the alkalizing agent.

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

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

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially when in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. However, the oxidation coloring agent can also be applied to the hair together with a catalyst which activates the oxidation of the dye precursors, for example by atmospheric oxygen. Such catalysts are, for example, transition metal compounds, iodides, quinones or certain enzymes. Suitable enzymes are, for example, peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for this, for example

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

Glucose oxidase and D-glucose,

Glycerin 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 salts thereof,

Choline oxidase and choline,

- Amino acid oxidase and amino acids. The agents according to the invention can furthermore contain all active substances, additives and auxiliary substances known for such preparations. In many cases, these agents contain at least one surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps )

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear one

Alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16,

Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,

Acyl taurides with 10 to 18 carbon atoms in the acyl group,

Acyl isethionates with 10 to 18 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the

Alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 C atoms, linear alpha olefin sulfonates with 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which

R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

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

The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl residues are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1- Stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R essentially consists of C ₈ and C ₁₀ alkyl groups, essentially C ₁₂ and C ₁₄ alkyl groups, essentially C ₈ -C ₆ alkyl groups or essentially C ₂ - Cι ₆ alkyl groups.

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

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

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention. The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COCOA or -SO ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxy imethy 1-3-hydroxyethyl imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and the cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming 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 with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-coconut alkylaminopropionate, the coconut acylaminoethylaminopropionate and the C _2-2 ₈ -acyl sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the compounds known under the INCI names Quaternium-27 and Quaternium-83 Imidazol. 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 sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, and Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

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

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

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow 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 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

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

Furthermore, the agents according to the invention can preferably also contain a conditioning active ingredient selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils. Cationic polymers can be preferred as conditioning agents. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldialylammonium chloride-acrylamide copolymer) and Merquat ^® 280

(Dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquatium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred. Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Coming under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow ^Coming® 929 emulsion (containing a hydroxyl-amino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt ; diquaternary polydimethylsiloxanes, Quaternium-80).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate acrylamide copolymers methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate crotonic acid copolymers, vinylpyrrolidone / 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. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, Starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,

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

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active substances which improve the fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-l-alkylamidoethyl-2 alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone 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, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those from groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, white dome, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root. Cholesterol, consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, Fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments,

Stabilizing agent for hydrogen peroxide and other oxidizing agents, blowing agents such as propane-butane mixtures, NO, dimethyl ether, CO ₂ and air, antioxidants.

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

A second subject of the invention is a process for dyeing keratin fibers, in particular hair, using an oxidation dye according to the invention. The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is rinsed off from the hair to be colored. Washing with a shampoo is not necessary if a carrier with a high tenside content, such as a coloring shampoo, has been used. A third object of the invention is also the use of compounds of the formula (I) as a coupler component in oxidation colorants for coloring keratin fibers, in particular hair.

The following examples are intended to clarify the subject matter of the present application.

Examples

To ending examples

1. Production of the coloring cream

Partial mixture A:

Hydreno ^ D ¹ 8.50 g

Loro techn. ² 2.00 g

Eumulgin ^® B2 ³ 0.75 g

Texapon ^® NSO ⁴ 20.00 g

Dehyton ^® K ⁵ 12.50 g

Water 30.00 g

C ₁₆ -C ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (COGNIS) Cι ₂ -Cι ₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS) Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth -20) (COGNIS)

Lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (COGNIS)

N, N-Dimethyl-N- (C ₈ -C ₁₈ cocosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

The substances Hydrenol ^® D, Lorol ^® and Eumulgin ^® B2 were melted at 80 ° C, mixed with the 80 ° C hot water containing Texapon ^® NSO and Dehyton ^® K, and emulsified with vigorous stirring. The emulsion was then cooled with gentle stirring. Partial mixture B

Sodium sulfite 1.00 g

Ammonium sulfate 1.00 g

Dye precursors each 2.5 mmol

Ammonia (25% solution) ad pH = 10.0

Water 10.00 g

The dye precursors were dissolved in the water at 50 ° C. with the addition of sodium sulfite, ammonium sulfite and ammonia.

The dye precursor solution (partial mixture B) was added to the emulsion (partial mixture A), adjusted to pH = 10 with ammonia and made up to 100 g with water. The stirring was continued until the room temperature was reached.

2. Coloring the fibers

The coloring cream obtained after 1 was mixed in a ratio of 2: 1 with a 3% H ₂ O ₂ solution and applied to 5 cm long strands of standardized, 80% gray, but not specially pretreated human hair (Kerling). After an exposure time of 30 minutes at 32 ° C., the hair was rinsed, washed out with a customary shampoo and then dried. The results are shown in Table I. Table I:

Example developer coupler obtained shade

2.1.1 El Kl deep violet 2.1.2 E2 K2 black blue 2.1.3 El K2 dark green 2.1.4 E3 K2 dark ruby 2.1.5 E4 K2 black blue 2.1.6 E5 K2 deep magenta 2.1.7 E6 K2 dark blue 2.1.8 E7 K2 dark violet

Developer components: El 2,4,5,6-tetraaminopyrimidine

E2 p-toluenediamine

E3 p-aminophenol

E4 2- (ß-Hydroxyethyl) -p-phenylenediamine

E5 4,5-diamino-1 - (2-hydroxyethyl) pyrazole

E6 l, 3-N, N'-bis (2-hydroxyethyl) - N, N'-bis (4-aminophenyl) diaminopropan-2-ol

E7 4-hydroxy-2,5,6-triamino-pyrimidine

Coupler components: Kl 7-hydroxy-l, 2,3,4-tetrahydroquinoline K2 7- amino-1, 2,3, 4-tetrahydroquinoline

For further colorations, the coloring cream obtained after 1 was used without additional oxidizing agent (air oxidation) or the coloring cream obtained after 1 was mixed in a ratio of 2: 1 with a 1% or 9% H ₂ O ₂ solution and was 5 cm long Strands of standardized, 80% gray, but not specially pretreated human hair (Kerling) applied. After an exposure time of 30 minutes at 32 ° C., the hair was rinsed, washed out with a customary shampoo and then dried. The results of the colorations are shown in Table II. speak received received received speak

Example developer coupler Nuance Nuance Nuance

Air oxidation 1% H ₂ O ₂ 9% H ₂ O ₂

2.2.1 E1 + E2 K2 dark blue black blue black blue

2.2.2 E2 + E7 K2 dark purple black blue black blue

2.2.3 E2 + E8 K2 gray ruby black blue black blue

2.2.4 E2 K2 + K3 dark blue black blue black blue

2.2.5 E9 K2 gray-brown violet-brown marron

2.2.6 E2 + E9 K2 purple gray black blue black blue

2.2.7 E3 + E4 K2 brown gray black blue dark purple

2.2.8 E4 K2 + K4 matt blue black blue black blue

2.2.9 E5 + E6 K2 dark purple dark purple dark purple

2.2.10 E6 K2 + K5 matt green dark blue dark blue

2.2.11 E10 K2 + K6 gray turquoise dark blue dark blue

Developer components: El 2,4,5,6-tetraaminopyrimidine

E2 p-toluenediamine

E3 p-aminophenol

E4 2- (ß-Hydroxyethyl) -p-phenylenediamine

E5 4,5-diamino-1 - (2-hydroxyethyl) pyrazole

E7 4-hydroxy-2,5,6-triamino-pyrimidine

E8 5,6-diamino-2,4-dihydroxypyrimidine

E9 bis (5-amino-2-hydroxyphenyl) methane

E 10 N, N-bis (2-hydroxyethyl) p-phenylene-diamine

Coupler components: K3 2-amino-3-hydroxypyridine

K4 1,3-bis (2 ', 4'-diaminophenoxy) propane

K5 2,4-diaminophenoxyethanol

K6 1-naphthol

Claims

claims

1. Coloring agent for dyeing keratin fibers, in particular human hair, containing at least one coupler component and at least one developer component in a medium suitable for dyeing, characterized in that it contains at least one compound of the formula (I) as a coupler component,

(I) in which

R stands for hydrogen, a dC ₄ -alkyl group, a -C-C ₄ -perfluoroalkyl group, a C ₂ -C ₄ -monohydroxyalkyl group, a C ₂ -C ₅ -polyhydroxyalkyl group, a C -

C ₄ alkylene group, a C ₂ -C aminoalkyl group, a benzyl group, a

Pipendinoalkyl group or a morpholinoalkyl group,

R ² , R ³ , R ⁴ and R ⁵ independently represent hydrogen or a dC ₄ -

Alkyl or perfluoroalkyl group,

R ⁶ and R ⁸ independently of one another represent hydrogen, halogen, a dC ₄ -

Alkoxy group, a C 1 -C ₄ -alkyl or perfluoroalkyl group, a dC ₄ -

Monohydroxyalkyl group or a C ₂ -C ₅ polyhydroxyalkyl group,

R ⁷ represents hydrogen, halogen or a C 1 -C ₄ alkoxy group,

A stands for a hydroxyl group or a -NR ⁹ R ¹⁰ group, where R ⁹ and R ¹⁰ independently of one another represent hydrogen, a dC ₄ -alkyl group, a C ₂ -C -

Monohydroxyalkyl group or a C ₂ -C ₄ polyhydroxyalkyl group

or contains one of the corresponding physiologically acceptable salts.

2. Composition according to claim 1, characterized in that A represents an NH ₂ group or a hydroxy group.

3. Composition according to one of claims 1 or 2, characterized in that R ¹ stands for hydrogen, a Cι-C ₄ - alkyl group, a benzyl group, a C ₂ -C ₄ alkenyl group or a C ₂ -C ₄ -monohydroxyalkyl group.

4. Composition according to one of claims 1 to 3, characterized in that R ⁶ , R ⁷ and R ⁸ are independently hydrogen, halogen or a C ₁ -C ₄ alkoxy radical

5. Composition according to one of claims 1 to 4, characterized in that R ² , R ⁴ and R ⁵ are hydrogen.

6. Composition according to one of claims 1 to 5, characterized in that the compound of formula (I) is 7-hydroxy-l, 2,3,4-tetrahydroquinoline or 7-amino-l, 2,3,4-tetrahydroquinoline ,

7. Composition according to one of claims 1 to 6, characterized in that it contains at least one developer component which is selected from a pyrimidine derivative, a pyrazole derivative, a p-aminophenol derivative or a p-diaminobenzene derivative.

8. Composition according to claim 7, characterized in that the developer component is selected from p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p- phenylenediamine, N, N-bis (ß-hydroxyethyl) -p- phenylenediamine, N, N'-bis- (ß-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -l, 3-diamino-propan-2-ol, bis- (2-hydroxy-5- aminophenyl) methane, N, N'-bis (4'-aminophenyl) -l, 4-diazacycloheptane, l, 10-bis (2 ', 5'-diaminophenyl) -l, 4,7,10-tetraoxadecane , p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, o-aminophenol, 4-amino-2-aminomethylphenol, 2-amino-5-methylphenol, 4-amino-2 - ((diethylamino ) methyl) phenol, 2-amino-4-methylphenol, 2-amino-4-chlorophenol, 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, 2,5, 6-triaminopyrimidine, 1 - (2 '-hydroxy-5' - aminobenzyl) -imidazolidin-2-one and 4,5-diamino-1 - (2'-hydroxyethyl ) pyrazole.

9. Composition according to claims 1 to 8, characterized in that it contains at least one further coupler component which is selected from 2-amino-3-hydroxypyridine, 2-amino-3-hydroxy-5-chloropyridine, 3-amino-2 -methylamino-6-methoxy-pyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, m-phenylenediamine, 2,6-bis (2-hydroxyethylamino) toluene , 3-amino-2,4-dichlorophenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5- (ß-hydroxyethyl) amino-2-methylphenol, 5-amino -2-methylphenol, 2-methylresorcinol, 2- (2 ', 4'-diaminophenoxy) ethanol, 1,3-bis (2', 4'-diamino-phenoxy) propane, resorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, m -Aminophenol, 1,7-, 2,7- and 1,5-dihydroxynaphthalene as well as 4-hydroxyindole and 6-hydroxyindole.

10. A process for dyeing keratin fibers, characterized in that an agent according to one of claims 1 to 9 is applied to the fibers and is removed from the fibers again after an exposure time.

11. Use of compounds of the formula (I), according to Claim 1, as a coupler in oxidation colorants for coloring keratin fibers.