DE10103160A1 - New and known hair dyes containing m-phenylenediamines give good results, especially with 2,4,5,6-tetraaminopyrimidine as developer - Google Patents

Abstract

The coupler component in a dyeing agent also containing a carrier and a developer component and used for keratinous fibers, especially human hair, is an m-phenylenediamine derivative (I) or its salts. Some (I) are claimed as new compounds. The coupler component in a dyeing agent also containing a carrier and a developer component and used for keratinous fibers, especially human hair, is an m-phenylenediamine derivative of formula (I) or its salts. A1 = H, benzyl, 2-4C alkenyl, 1-4C alkyl or monohydroxyalkyl or 2-4C polyhydroxyalkyl; B1, C1 = H or 1-4C alkyl; R1 = H, halogen, 1-4C alkyl, monohydroxyalkyl or alkoxy or 2-4C polyhydroxyalkyl; R2-R4 = H, halogen, 1-4C alkyl, perfluoroalkyl, monohydroxyalkyl or alkoxy or 2-4C polyhydroxyalkyl, with the proviso that at least one of R2-R4 = H, halogen or 1-4C alkoxy; X = pyridyl or C6H3R5R6; R5, R6 = H, OH, halogen, sulfonic acid or 1-4C alkyl or alkoxy; and n = 1-4.

Description

The invention relates to agents for dyeing keratin fibers, the special derivatives of m Phenylendiamine as a coupler component in combination with at least one Developer component, a method for dyeing keratin fibers with these Means, the use of the dye combinations according to the invention for the dyeing of Keratin fibers and new m-phenylenediamine derivatives.

Under keratin fibers according to the invention are furs, wool, feathers and in particular the understood human hair. Human hair is involved in many ways today treated hair cosmetic preparations. These include cleaning the hair with Shampoos, the care and regeneration with rinses and cures and bleaching, Dyeing and shaping of hair with coloring, tinting, waving and Styling preparations. Thereby means for changing or nuancing the color of the Head hair a prominent role.

For temporary dyeings usually dyeing or tinting agents are used, which as coloring component so-called Direktzieher included. This is Dye molecules that grow directly on the hair and no oxidative process for Need training of the paint. For example, one of these dyes already belongs Henna known in antiquity for coloring body and hair. These dyes are Shampooing usually sensitive, so that often undesirable Shade shift or even a visible "discoloration" may occur.

For the dyeing of keratin fibers, especially hair, play the so-called Oxidation colorants because of their intense colors and good fastness properties, the be achieved at relatively low dyeing temperature and in short dyeing times, a  special role. Such colorants contained in a suitable, usually aqueous carrier a developer component which is under the influence of atmospheric oxygen or of Oxidants by oxidative coupling forms the dye. This dye can by coupling with another developer component or with so-called Coupler components, which themselves can not form dyes, intensified and in the Nuance be modified.

Good oxidation dye precursors are primarily the following prerequisites You must: In the oxidative coupling you have the desired color shades in form sufficient intensity and authenticity. You also need a good one Have Aufziehvermögen on the fiber, in particular, in human hair no noticeable differences between strained and freshly regrowed hair may (leveling). They should be resistant to light, heat, friction and the Influence of chemical reducing agents, eg. B. permanent wave fluids. Finally, should - if used as a hair dye - the scalp does not stain too much, and Above all, they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloring achieved by bleaching should be easily removed from the hair again if they do not meet the individual wishes of the individual corresponds and should be reversed.

For hair dyeing and tinting agents in particular the shades in red and Brown area of a significant importance, since they are used to produce natural Hair dyeing is mandatory. Oxidation dyes in red and brown, as they are z. B. with the combination of 2,4,5,6-tetraaminopyrimidine and 2-methylresorcinol are not yet optimal in terms of uniformity of the paint elevator on. Direct dyes are usually less washfast and therefore not so good at Combination with oxidation dyes suitable.

For these reasons, there is a need for novel oxidation dye precursors which especially when using 2,4,5,6-tetraaminopyrimidine as a developer To allow improvement of the above parameters. Surprisingly found that certain m-phenylenediamine derivatives meet the above requirements in excellently meet.  

A first subject of the invention is therefore an agent for dyeing keratin fibers, in particular hair, which contains at least one developer component and at least one coupler component in a carrier suitable for dyeing, characterized in that the coupler component is an m-phenylenediamine derivative of the formula I or its corresponding physiologically acceptable salt, is included

in which

• A is hydrogen, benzyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl,
• B and C independently of one another represent hydrogen or a C ₁ -C ₄ -alkyl group,
• - R ¹ represents hydrogen, halogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ - monohydroxyalkyl, a C ₂ -C ₄ polyhydroxyalkyl or C ₁ -C ₄ - alkoxy group,
• - R ² , R ³ and R ⁴ are hydrogen, halogen, a C ₁ -Ca-alkoxy, a C ₁ -C ₄ - alkyl or perfluoroalkyl, a C ₁ -C ₄ -Monohydroxyalkylgruppe or a C ₂ - C ₄ Polyhydroxyalkyl group, with the proviso that at least one of the radicals R ² or R ⁴ is hydrogen, halogen or a C ₁ -C ₄ alkoxy radical,
• - X is a pyridyl radical or -C ₆ H ₃ R ⁵ R ⁶ , wherein R ⁵ and R ⁶ are independently hydrogen, a hydroxy, a halogen, a sulfo group, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group,
• - n is an integer from 1 to 4.

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, with vinyl and allyl being particularly preferred. Preferred C ₁ -C ₄ -monohydroxyalkyl groups are the groups hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-hydroxyethyl is a particularly preferred hydroxyalkyl group. Preferred C ₂ -C ₄ polyhydroxyalkyl groups are α, β-dihydroxyethyl and β, γ-dihydroxypropyl. Suitable halogen substituents according to the invention are preferably chlorine, bromine and iodine, particularly preferred are chlorine and bromine. Physiologically acceptable salts include salts of inorganic or organic acids, eg. B. Hydrochlori de, sulfates or hydrobromides understood.

Preference is given to compounds of the formula I in which A is hydrogen, a vinyl, allyl or is a benzyl group.

Furthermore, compounds of the formula I are preferred in which n = 1 or 2; especially preferably n = 1.

Also preferred are compounds of formula I wherein R ¹ represents hydrogen, a C ₁ - C ₄ alkyl group or a C ₂ -C ₄ monohydroxyalkyl stands. Hydrogen and the methyl group are particularly preferred.

The compounds of the formula I are preferred according to the invention in which at least 2 of the substituents R ² , R ³ or R ^{4 are} hydrogen, halogen or a C ₁ -C ₄ alkoxy group. Hydrogen, chlorine, bromine, methoxy or ethoxy are particularly preferred. Hydrogen is very particularly preferred.

Particularly preferred m-phenylenediamine derivatives of the formula I are N, N'-dibenzyl- m-phenylenediamine and N-benzyl-m-phenylenediamine.

The preparation of the m-phenylenediamine derivatives of the formula I, for example of N-benzyl-m-phenylenediamine, takes place by known processes of organic synthesis, preferably in such a way that an appropriately substituted m-nitroaniline derivative is condensed with an aldehyde. Subsequently, the resulting imine is to be reduced with NaBH ₄ to form the secondary amine. The nitro group is reduced by known methods to the NH ₂ group (Huneck et al., J. Plant Growth Regul. (1984), 3, 75.).

The synthesis of N, N'-substituted m-phenylenediamine derivatives is analogous to that in The synthetic route described in the literature (Klee et al., Macromol Chem. Phys., (1996), 197, 2305.).

In addition to the m-phenylenediamines according to the invention, the agents according to the invention contain at least one developer component. As developer components are usually primary aromatic amines with another, 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.

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

in which

• - G ¹ represents a hydrogen atom, a C ₁ -C ₄ alkyl, C ₁ -C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy (C ₁ - C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ -C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical,
• G ² represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -mohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a (C ₁ -C ₄ ) -alkoxy- (C ₁ C ₄ ) -alkenyl or a C ₁ -C ₄ -alkyl radical which is substituted by a nitrogen-containing group,
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -Ca-monohydroxyalkyl radical, a C ₂ -C ₄ -hydroxyalkyl radical, a C ₁ -C ₄ -Hydroxyalkoxyrest, a C ₁ -C ₄ - Acetylaminoalkoxyrest, a C ₁ -C ₄ -Mesylaminoalkoxyrest or a C ₁ -C ₄ - Carbamoylaminoalkoxyrest,
• G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₄ -alkyl radical or
• when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ -C ₄ -alkyl radicals mentioned as substituents in the context of this application are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Examples of preferred C ₂ -C ₄ -alkenyl radicals are vinyl and allyl. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ -C ₄ monohydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. An example of a preferred C ₂ -C ₄ polyhydroxyalkyl group is the α, β-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 formula (II) are especially the amino groups, C ₁ -C ₄ monoalkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ - trialkylammonium groups, C ₁ -C ₄ -Monohydroxyalkylaminogruppen, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p- Phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p- phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5- Dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p- phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-  phenylenediamine, 2-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.

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

It may further be preferred according to the invention, as the developer component compounds containing at least two aromatic nuclei containing amino and / or Hydroxyl groups are substituted.

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 -C 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,
• - 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 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 substituted by one or more hydroxyl or C ₁ -C ₈ alkoxy radicals, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a direct connection to the bridge Y,
• G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ -C ₄ -alkyl radical,
  with the provisos that
• The compounds of the formula (E2) contain only one bridge Y per molecule and
• - The compounds of formula (E2) contain at least one amino group, which carries at least one hydrogen atom.

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

Preferred binuclear developer components of the formula (E2) are in particular: N, N'- Bis- (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-) hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetra methylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4'-amino) 3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-bis) aminophenyl) -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.

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

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

in which

• - G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl, C ₁ -C ₄ - monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy- ( C ₁ -C ₄₎ - alkyl group, a C ₁ -C ₄ aminoalkyl radical, a hydroxy (C ₁ -C ₄₎ alkylamino group, a C ₁ -C ₄ -Hydroxyalkoxyrest, a C ₁ -C ₄ hydroxyalkyl ( C ₁ - to C ₄ ) -aminoalkyl or a (di-C ₁ -C ₄ -alkylamino) - (C ₁ -C ₄ ) -alkyl radical, and
• - G ¹⁴ represents a hydrogen or halogen atom, a C ₁ -C ₄ alkyl, C ₁ -C ₄ - hydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄₎ alkoxy- (C ₁ -C ₄₎ - alkyl group, a C ₁ -C ₄ aminoalkyl radical or a C ₁ -C ₄ -Cyanoalkylrest,
• - G ¹⁵ is hydrogen, a C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl radical, a C ₂ - 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 analogous to the above according to the invention Executions defined.

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-hydroxy methylamino-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- (β- hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-  Dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physiological compatible salts.

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

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

Furthermore, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole Pyrimidine derivatives and their physiologically acceptable salts. To be favoured According to the invention pyrimidine or pyrazole derivatives.

Preferred pyrimidine derivatives are in particular the compounds described in the German patent DE 23 59 399, Japanese Patent Laid-Open JP 02019576 A2 or in the Laid-open WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4- Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, EP-740931 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-yl hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-  triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4 (β- hydroxyethyl) amino-1-methylpyrazole.

Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4- Methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β- Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

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

in which:

• - G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a C ₁ - C ₄ alkyl radical, an aryl radical, a C ₁ -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl a (C ₁ -C ₄ ) -alkoxy (C ₁ -C ₄ ) -alkyl radical, a C ₁ -C ₄ -aminoalkyl radical which may optionally be protected by an acetyl-ureide or sulfonyl radical, a (C ₁ C ₄ ) -Alkylamino- (C ₁ -C ₄ ) -alkyl radical, a di - [(C ₁ -C ₄ ) -alkyl] - (C ₁ -C ₄ ) -aminoalkyl radical, wherein the dialkyl radicals optionally have one carbon cycle or a heterocycle with 5 or 6 chain members, form a C ₁ - C ₄ hydroxyalkyl or a di- (C ₁ -C ₄₎ - [hydroxyalkyl] - (C ₁ -C ₄₎ aminoalkyl radical,
• - the X radicals are each independently a hydrogen atom, a C ₁ -C ₄ - alkyl radical, an aryl radical, a C ₁ -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ - polyhydroxyalkyl radical, a C ₁ -C ₄ -Aminoalkylrest, a (C ₁ -C ₄ ) -Alkylamino- (C ₁ -C ₄ ) alkyl radical, a di - [(C ₁ -C ₄ ) alkyl] - (C ₁ -C ₄ ) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ -C ₄ -hydroxyalkyl or a di (C ₁ -C ₄ -hydroxyalkyl) - aminoalkyl, an amino radical, a C ₁ -C ₄ Alkyl or di (C ₁ -C ₄ hydroxyalkyl) amino, halogen, carboxylic acid or 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 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 according to the invention analogous to the above Executions defined.

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

In particular, among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4):

• - pyrazole [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole (1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-7-ol;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-5-ol;
• - 2- (3-amino-pyrazolo [1,5-a] -pyrimidin-7-ylamino) -ethanol;  
• - 2- (7-amino-pyrazolo [1,5-a] -pyrimidin-3-ylamino) -ethanol;
• - 2 - [(3-amino-pyrazolo [1,5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-amino-pyrazolo [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;
• 2,5, N7, N7-tetramethylpyrazolo [1,5-a] -pyrimidine-3,7-diamine;

and their physiologically acceptable salts and their tautomeric forms, when tautomeric equilibrium is present.

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

Developer components preferred according to the invention are pyrimidine derivatives, Pyrazole derivatives, p-aminophenol derivatives and p-phenylenediamine derivatives.

Particularly preferred developer components according to the invention are p-phenylenediamine, p- Toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p- phenylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propane 2-ol, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4'-aminophenyl) -1,4- diazacycloheptane, 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4- Amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol 4-amino-2- ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5- 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.

Very particularly preferred developer components according to the invention are p-toluenediamine and 2,4,5,6-tetraaminopyrimidine.

Alone with a developer component or a special coupler / developer As a rule, it is not possible to achieve a natural color shade on the hair  to obtain. In practice, therefore, usually combinations of different Developer and / or coupler components used. There is therefore a constant need for new, improved dye combinations. As further coupler components According to the invention in particular m-phenylenediamine derivatives, naphthols, resorcinol and Resorcinol derivatives, pyrazolones, and m-aminophenols.

According to the invention, additional preferred coupler components are

• 1. 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,
• 2. o-aminophenol and its derivatives,
• 3. m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) - benzene, 1,3-bis (2 ', 4'-diaminophenyl) propane, 2,6-bis- (2'-hydroxyethylamino) -1- methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• 4. o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• 5. 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,
• 6. Pyridine derivatives such as, for example, 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,
• 7. 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,  
• 8. morpholine derivatives such as 6-hydroxybenzomorpholine and 6-amino benzomorpholine,
• 9. quinoxaline derivatives such as, for example, 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• 10. pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• 11. indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• 12. 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
• 13. methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1 Amino-3,4-methylenedioxybenzene and 1- (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- (β-hydroxyethyl) amino-2-methylphenol, 5-amino-2-ol 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 and 4-hydroxyindole and 6-hydroxyindole.

The hair colorants of the invention contain both the developer components as also the coupler components preferably in an amount of 0.005 to 10 wt .-% preferably from 0.1 to 5 wt .-% in each case based on the total oxidation colorant.

In this case, developer components and coupler components are generally approximately used molar amounts to each other. If the molar use as appropriate has proven, so is a certain excess of individual oxidation dye precursors not disadvantageous, so that developer components and coupler components in a mole Ver ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, may be included.  

Furthermore, the agents according to the invention precursors of natural dyes contain. As precursors of naturally-analogous dyes are preferred such indoles and Indolines are used, the at least one hydroxy or amino group, preferably as Substituent on the six-membered ring. These groups may carry further substituents, e.g. B. in the form of an etherification or esterification of the hydroxy group or an alkylation of Amino group.

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

in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ - C ₄ alkenyl group or a C ₁ -C ₄ hydroxyalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ in which
R ⁶ is a C ₁ -C ₄ alkyl group, and
R ⁵ represents one of the groups mentioned under R ⁴ ,
and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are the 5,6-dihydroxyindohin, 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, the 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 the 5,6-dihydroxyindoline.

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

in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ - C ₄ alkenyl group or a C ₁ -C ₄ hydroxyalkyl group,
R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ in which
R ⁶ is a C ₁ -C ₄ alkyl group, and
R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

Within this group, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6- dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and especially in particular the 5,6-dihydroxyindole.  

The indoline and indole derivatives can be used in the colorants according to the invention both as free bases as well as in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides used become. The indole or indoline derivatives are usually present in amounts of 0.05-10 Wt .-%, preferably 0.2-5 wt .-%.

Especially in the use of dye precursors of the indoline or indole type it has proved to be advantageous as alkalizing an amino acid and / or a Use oligopeptide.

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

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols. Preferred substantive dyes are under 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 known compounds as well as 1,4-diamino-2-nitrobenzene, 2- Amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-) hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'- Hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) -amino-5-chloro-2 nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2- nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4- naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4- Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are

• a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• b) aromatic systems substituted with a quaternary nitrogen group, such as for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well
• c) direct dyes containing a heterocycle containing at least one has quaternary nitrogen atom, as described for example in EP-A2-998 908, to the is explicitly referred to at this point, called in claims 6 to 11 become.

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

The compounds of formulas (DZ1), (DZ3) and (DZ5) are most preferred cationic substantive dyes of group (c).

The agents according to the invention according to this embodiment contain the substantive Dyes preferred in an amount of 0.01 to 20 wt .-%, based on the total Colorant.

Furthermore, the preparations according to the invention can also occur in nature Dyes contain, for example, in henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and Alkana root are included.

The inventive compositions contain dye precursors preferably 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 that Dye precursors in a powdered or tablet-shaped formulation too integrate.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alcohol, 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 when in addition to the coloring, a lightening effect on human hair is desired. As oxidation Persulfates, chlorites and in particular hydrogen peroxide or its An Storage products of urea, melamine and sodium borate in question. It continues possible to carry out the oxidation by means of enzymes, wherein the enzymes for both Generation of oxidizing per-compounds are used as well as for reinforcement the effect of a small amount of oxidizing agent present. So can the enzymes (Enzyme class 1: oxidoreductases) Electrons from suitable developer components (Reducing agent) transferred to atmospheric oxygen. Oxidases such as Tyrosinase, ascorbate oxidase and laccase but also glucose oxidase, uricase or Pyruvate. Furthermore, the procedure is called the effect of small amounts (eg. 1% and less, based on total agent) of hydrogen peroxide by peroxidases strengthen.

The agents according to the invention can furthermore all be known for such preparations Active substances, additives and auxiliary substances. In many cases, these remedies contain at least a surfactant, whereby in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be proved to be advantageous, the surfactants from anionic, zwitterionic or nonionic Select surfactants.

Suitable anionic surfactants in preparations according to the invention are all films which are suitable for use on the human body, anionic surface-active substances. These are characterized by a water-solubilizing, anionic group such. Example, a 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 as well as the mono-, di- and trialkanolammonium salts having 2 or 3 C atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• - Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 18 carbon atoms in the Alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 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 having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether 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, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 8 to 22 C Represent 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. As a polyol group, a Po lyalkylenglykolethergruppe or a combination of polyol and Polyglykolethergruppe. Such compounds are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 C atoms, to fatty acids having 12 to 22 C atoms and to alkylphenols having 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated Ri zinusöl.

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

The alkyl radical R 'contains from 6 to 22 carbon atoms and can be both linear and branched his. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-octyl. Stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. Using so-called "oxo-alcohols" as starting materials predominate compounds with an unge number of carbon atoms in the alkyl chain.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are made 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.

Particularly preferred are those alkyl polyglycosides in which R '

• consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Substituted from C ₈ -C ₁₆ alkyl groups or
• - Consists essentially of C ₁₂ -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. Quite be particularly preferred are alkyl glycosides in which x is 1.1 to 1.4.

The alkyl glycosides can also serve, in addition to their surfactant effect, the fixation of Improve fragrance components on the hair. The expert will therefore in the event that an over the duration of the hair treatment going beyond effect of the perfume oil on the Hair is desired, preferably to this class of substance as a further ingredient of he resort to inventive preparations.

The alkoxylated homologs of said alkylpolyglycosides can also be invented be used according to. These homologs can average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium-glycinate, for example cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyl-dime thylammoniumglycinat, and 2-Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhy droxyethylcarboxymethylglycinat. 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 those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and enable the formation of internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, coco acylaminoethylaminopropionate and C _12-18 acyl sarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, in particular Chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, z. Cetyltrimethylammonium chloride, stea ryltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethyl ammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants mentioned preferably have 10 to 18 carbon atoms.

Esterquats are known substances which have 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 will be For example, sold under the trademarks Stepantex®, Dehyquart® and Armocare®. The products Armocare® VGH-70, an N, N-bis (2-palmitoyloxy  ethyl) dimethyl ammonium chloride, and Dehyquart® F-75 and Dehyquart® AU-35 Examples of such esterquats.

The alkylamidoamines are usually made by amidation of natural or synthetic Fatty acids and fatty acid sections prepared with dialkylaminoamines. An invention particularly suitable compound from this group of substances that under the name Tegoamid® S18 is commercially available stearamidopropyl-dimethylamine.

Further cationic surfactants which can be used according to the invention are the quaternized Protein hydrolysates.

Likewise suitable according to the invention are cationic silicone oils, such as those described in US Pat Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-mo modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (Her steller: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

An example of a cationic surfactant usable 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 be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one Substance mixtures with different alkyl chains depending on the respective raw material length receives.

For the surfactants, the adducts of ethylene and / or propylene oxide to fat represent alcohols or derivatives of these addition products, both products with a "normal" homolog distribution as well as those with a narrow homologue distribution can be used. Under "normal" homolog distribution Mi  understood by homologues, which are used in the reaction of fatty alcohol and Al ketylene oxide using alkali metals, alkali metal hydroxides or Alkalime obtains tallalkoholaten as catalysts. Narrow homolog distributions are opposed obtained, for example, when hydrotalcites, alkaline earth metal salts of ether carboxylic acids, Erd alkali metal oxides, hydroxides or alcoholates are used as catalysts. The Use of products with narrow homolog distribution may be preferred.

Furthermore, the agents according to the invention can preferably also have a conditioning Active ingredient selected from the group consisting of cationic surfactants, cationic Polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed.

Cationic polymers may be preferred as conditioning agents. These are in usually polymers containing a quaternary nitrogen atom, for example in the form of an Am monium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as they are known under the names Celquat® and Po lymer JR® are commercially available. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• - Dimethyldiallylammoniumsalze polymeric 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 (dimethyldial lylammonium chloride-acrylamide copolymer) and Merquat® 550 (Dimethyldiallylammonium chloride-acrylic acid copolymer commercially available Products are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylate, such as vinylpyrrolidone quaternized with diethyl sulfate. Dimethylaminomethacrylate copolymers. Such compounds are among the Designations Gafquat®734 and Gafquat®755 commercially available.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, as described under the name Luviquat®.
• - Quaternized polyvinyl alcohol

as well as those under the designations  

• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymerhauptkette.

Particularly preferred are cationic polymers of the first four groups, completely Polyquaternium-2, polyquaternium-10 and polyquaternium-22 are particularly preferred.

Further suitable conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes such as dimethylpolysiloxane and methylphenylpolysi loxan, as well as their alkoxylated and quaternized analogs. Examples of such silicones are those of Dow Coming under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing hydroxylamino-modified silicone, also referred to as amodimethicones), SM- 2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

Also usable as conditioning agents are paraffin oils, synthetically prepared oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, Almond oil, wheat germ oil and peach kernel oil.

Likewise suitable hair conditioning compounds are phospholipids, for example Soy lecithin, egg lecithin and cephaline.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Zwitterionic and amphoteric polymers such as acrylamidopropyl tri methyl ammonium chloride / acrylate copolymers and octylacrylamide methyl methacrylate lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,  
• Anionic polymers such as, for example, 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 acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, 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. B. Bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, egg Lecitin and Kephaline,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids as well quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, Glycerine and diethylene glycol,
• - Fiber structure improving agents, in particular mono-, di- and oligosaccharides such for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - Sunscreens, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• - Substances for adjusting the pH, such as conventional acids, in particular special 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, Quendel, Yarrow, Thyme, Melissa, Hauhechel, 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
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding further optional components as well as the amounts of this com Components are expressly based on the specialist manuals known to those skilled in the art, eg. B. K. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

A second aspect 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 immediately before use Mixture of the preparation of the oxidizing agent with the preparation containing the color Stoffvorprodukte, manufactured. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the Application of hair dye in a weak alkaline environment. The application terms  temperatures can range between 15 and 40 ° C. After a Einwir From 5 to 45 minutes, the hair dye is removed by rinsing removing coloring hair. The Nachwaschen with a shampoo is eliminated if a strong ten Sidhaltiger carrier, z. As a dyeing shampoo was used.

A third object of the invention is the use of compounds of the formula (I) as a coupler component in oxidation dyes for dyeing keratin fibers, especially of hair.

New and thus a fourth subject of the invention are the compounds N-benzyl-2 methyl-m-phenylenediamine, N, N'-dibenzyl-2-methyl-m-phenylenediamine, N, N'-di (2'-methyl) phenylethyl) -2-methyl-m-phenylenediamine, N, N'-di (2'-phenylethyl) -m-phenylenediamine, N, N'- Dibenzyl-4-chloro-m-phenylenediamine, N, N'-dibenzyl-4,6-dichloro-m-phenylenediamine, N- Benzyl 4-chloro-m-phenylenediamine, N-benzyl-4,6-dichloro-m-phenylenediamine and N-benzyl N ', N'-dimethyl-m-phenylenediamine.

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

Examples 1st Synthesis Example Synthesis of N-benzyl-2-methyl-m-phenylenediamine.2HCl a) N-Benzyl-2-methyl-3-nitroaniline

The procedure is similar to the synthesis of N-benzyl-3-nitroaniline (J. Org. Chem., (1957), 22, 1070.) using 2-methyl-3-nitroaniline. 30.4 g (0.2 mol) of 2-methyl-3-nitroaniline and 42.1 g (0.4 mol) of benzaldehyde were stirred at 120-130 ° C over a period of 5 h. It was then allowed to cool to room temperature and the solution was concentrated. The resulting oil was allowed to crystallize at ca. 4 ° C. After renewed recrystallization from EtOH / H ₂ O (1: 1) and drying, 28.8 g (0.12 mol) of N-benzal-2-methyl-3-nitroaniline were obtained as a light yellow powder. 24.0 g (0.10 mol) of this powder were dissolved in 450 mL of absolute methanol. Over a period of 20 minutes, 4.2 g (0.11 mol) of NaBH _{4 were} added portionwise to the solution. The reaction mixture was stirred at room temperature for about 20 minutes and then at reflux for 15 minutes. Volatile was removed in vacuo. This gave N-benzyl-2-methyl-3-nitroaniline as a yellow crude product, which is used directly in step b).

b) N-Benzyl-2-methyl-m-phenylenediamine.2HCl

The crude product from stage a) was admixed with 400 ml of absolute ethanol. Insolubles were separated and the filtrate was treated with 1.7 g of palladium on charcoal (5% Pd / C). In a shaking flask, the reaction mixture was reacted in the presence of H ₂ (1 atm) for 20 h. Subsequently, 150 ml of a dilute aqueous HCl solution were added and filtered. Volatile was distilled off. The resulting orange oil was allowed to crystallize at ca. 4 ° C. This gave 10.6 g (0.04 mol) of N-benzyl-2-methyl-m-phenylenediamine.2HCl as light orange crystals.
Mp = 158-168 ° C

2. Application examples I) Preparation of the coloring cream Partial mixture A

Hydrenol®D ¹ 8.50 g Lorol®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 ¹ C ₁₆ -C ₁₈ fatty alcohol (INCI name: cetearyl alcohol) (COGNIS) @ ² C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS) @ ³ Cetearylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (COGNIS) @ ⁴ lauryl ether sulfate, sodium salt (about 27.5% active ingredient; (INCI name: Sodium Laureth Sulfate) (COGNIS) @ ⁵ N, N-dimethyl-N- (C ₈ -C ₁₈ -cocosamidopropyl) ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

The substances Hydrenol®D, Lorol® and Eumulgin®B2 were melted at 80 ° C, with the 80 ° C hot water containing Texapon®NSO and Dehyton® K, mixed and emulsified with vigorous stirring. Thereafter, the emulsion was stirred gently cooled.

Partial mixture B

sodium 1.00 g ammonium sulfate 1.00 g dye precursors in each case 7.5 mmol Ammonia (25% solution) ad pH = 10.0 water 10.00 g

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

The dye precursor solution (sub-mixture B) became the emulsion (sub-mixture A) adjusted with ammonia to pH = 10 and made up to 100 g with water. It was stirred until reaching room temperature.

II) staining of the fibers

The dyeing cream obtained according to I) was mixed in a ratio of 2: 1 with a 1% H ₂ O ₂ solution and applied to 5 cm strands of standardized human hair (Kerling) which was 80% gray, but not specially pretreated. After 30 minutes exposure time at 32 ° C, the hair was rinsed, washed with a conventional shampoo and then dried.

The results are shown in Table I.

Developer components:
E1 p-toluenediamine
E2 2,4,5,6-tetraaminopyrimidine
E3 p-aminophenol
E4 4,5-diamino-1- (2-hydroxyethyl) pyrazole
E5 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (3-aminophenyl) -diaminopropan-2-ol
E6 4-amino-3-methylphenol
E7 4-amino-3-fluorophenol
E8 4-hydroxy-2,5,6-triaminopyrimidine
E9 2- (β-hydroxyethyl) -p-phenylenediamine
E10 bis (2-hydroxy-5-aminophenyl) methane
E11 4-amino-2-aminomethylphenol

Intermediates:
K1 N, N'-Dibenzyl-m-phenylenediamine
K2 N-Benzyl-m-phenylenediamine.2HCl
K3 N-Benzyl-2-methyl-1,3-phenylenediamine.2HCl

Claims (13)

1. A colorant for dyeing keratin fibers, in particular human hair, comprising, in a vehicle suitable for dyeing, at least one coupler component and at least one developer component, characterized in that it comprises as coupler component at least one compound of the formula (I)
wherein

• A is hydrogen, benzyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl,
• B and C independently of one another represent hydrogen or a C ₁ -C ₄ -alkyl group,
• - R ¹ represents hydrogen, halogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ - monohydroxyalkyl, a C ₂ -C ₄ polyhydroxyalkyl or C ₁ -C ₄ - alkoxy group,
• R ² , R ³ and R ⁴ are hydrogen, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl or perfluoroalkyl, C ₁ -C ₄ monohydroxyalkyl or C ₂ -C ₄ -polyhydroxyalkyl group, with the proviso that at least one of the radicals R ² or R ⁴ is hydrogen, halogen or a C ₁ -C ₄ alkoxy radical,
• - X is a pyridyl radical or -C ₆ H ₃ R ⁵ R ⁶ , wherein R ⁵ and R ⁶ are independently hydrogen, a hydroxy, a halogen, a sulfone group, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group,
• - n is an integer from 1 to 4
  or one of the corresponding physiologically acceptable salts.

2. Composition according to claim 1, characterized in that A is hydrogen, a Vinyl group, an allyl group or a benzyl group. 3. Composition according to one of claims 1 or 2, characterized in that n has the value 1. 4. Composition according to one of claims 1 to 3, characterized in that R ¹ is hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ -Monohydroxyalkylgruppe. 5. Composition according to one of claims 1 to 4, characterized in that at least 2 of the substituents R ² , R ³ and R ^{4 are} selected from the group comprising hydrogen, halogen or a C ₁ -C ₄ alkoxy group. 6. Composition according to one of claims 1 to 5, characterized in that the compound of the formula (I) is N, N'-dibenzyl-m-phenylenediamine or N-benzyl-m-phenylenediamine. 7. Composition according to one of claims 1 to 6, characterized in that it has at least one Developer component which is selected from a Pyrimidinderivat, a Pyrazole derivative, a p-aminophenol derivative or a p-phenylenediamine derivative. 8. Composition according to claim 7, characterized in that the developer component is selected from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p- phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis- (β-) Hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5- aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, 1,10-bis- (2 ', 5'- diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4- Amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2- ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5- 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'-methyl) hydroxyethyl) pyrazole. 9. Composition according to claim 8, characterized in that the developer component is selected from p-tolylenediamine or 2,4,5,6-tetraaminopyrimidine. 10. Composition according to claims 1 to 9, characterized in that it has at least one contains 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- (β-hydroxyethyl) amino-2- methylphenol, 5-amino-2-methylphenol, 2-methylresorcinol, 2- (2 ', 4'- Diaminophenoxy) ethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, resorcinol, 4- Chlororesorcinol, resorcinol monomethyl ether, m-aminophenol, 1,7-, 2,7- and 1,5- Dihydroxynaphthalene and 4-hydroxyindole and 6-hydroxyindole. 11. A method for dyeing keratin fibers, characterized in that an agent one of claims 1 to 10 is applied to the fibers and after a contact time is removed again from the fibers. 12. Use of compounds according to formula (I), according to one of claims 1 to 6 than Coupler component in oxidation dyes for dyeing keratin fibers. 13. Compounds according to formula (I) according to claim 1, characterized by the following substituent combinations (i) to (ix):