DE10237816A1 - New acetal-containing p-phenylenediamine derivatives and their intermediates, useful as developers for oxidation dyeing of keratin, particularly human hair - Google Patents

Abstract

Acetal-containing p-phenylenediamine derivatives (I) are new. Acetal-containing p-phenylenediamine derivatives of formula (I) are new. R1 = hydrogen, 1-4C alkyl (optionally substituted by one hydroxy or 1-4C alkoxy), 2-4C polyhydroxyalkyl or halo; R2 and R3 = as R1 or the group -X-CH(OR4)(OR5) (II); X = 1-5C alkylene, optionally substituted by a 1-4C alkyl or alkoxy, hydroxy or halo; and R4 and R5 = 1-4C alkyl or together complete a 5 or 6-membered saturated ring, optionally substituted by 1-4C alkyl. At least one of R2 and R3 must be group (II) An Independent claim is also included for the 4-nitro-aniline derivatives of formula (I') provided that when R1 and R2 are both hydrogen and X is methylene, then R4 and R5 are not both methyl.

Description

The present invention relates to new p-phenylenediamine derivatives which are attached to a nitrogen atom with a Are substituted alkyl group that carries an acetal function, hair dye, that contain them, as well as intermediates that are used in the manufacture of these connections arise.

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

As developer components are usually primary aromatic amines with another, in para or ortho position located, free or substituted hydroxyl or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives as well as 2,4,5,6-tetraaminopyrimidine and its derivatives.

Special representatives are, for example p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) ethanol, 2- (2', 5'-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-aminophenyl) diamino-propan-2-ol.

As coupler components are in usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, Pyrazolone and m-aminophenols used. Suitable as coupler substances particularly 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chloronesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Good oxidation dye precursors should primarily meet the following requirements: the desired oxidative coupling Develop color shades with sufficient intensity and authenticity. she have to also good windability own on the fiber, especially with human hair no noticeable differences between stressed and fresh regrown hair may exist (Leveling). They are said to be constant be against light, warmth, sweat, Friction and the influence of chemical reducing agents, e.g. Perm liquids. Finally should - if as a hair dye coming into use - the Don't stain your scalp too much, and above all, they should be toxicological and dermatological Be harmless. Furthermore, the coloring achieved by bleaching can be easily removed from the hair if it is not the individual wishes corresponds to the individual person and should be undone.

Alone with a developer component or a special coupler / developer combination succeeds in usually not to give a natural shade to the hair receive. In practice, therefore, combinations are usually used various developer and / or coupler components used. It is therefore permanent Need for new, improved dye components that are also in toxicological and dermatological aspects are unproblematic.

Object of the present invention was therefore to develop new developer components that the requirements placed on oxidation dye precursors, in particular in terms of toxicological and dermatological properties, fulfill and coloring enable in a wide range of colors with good fastness properties.

Surprisingly it has now been found that p-phenylenediamine derivatives which can be treated with a Alkyl chain substituted acetal group, the on oxidation dye precursors to a high degree. The developer components according to the invention are characterized by brilliant coloring, high color intensity and excellent Authenticity.

wobei
R¹ steht für ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe, eine C₁- bis C₄-Monohydroxyalkylgruppe, eine C₂- bis C₄- Polyhydroxyalkylgruppe, eine C₁- bis C₄-Alkoxy-(C₁- bis C₄)-alkylgruppe oder ein Halogenatom und
R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe, eine C₁- bis C₄-Monohydroxyalkylgruppe, eine C₂- bis C₄-Polyhydroxyalkylgruppe, eine C₁- bis C₄-Alkoxy-(C₁- bis C₄)-alkylgruppe oder einen Rest der Formel (II)

wobei
X steht für eine C₁- bis C₅-Alkylengruppe, die gegebenenfalls mit einer C₁- bis C₄-Alkylgruppe, einer Hydroxygruppe, einer C₁- bis C₄-Alkoxygruppe oder einem Halogenatom substituiert sein kann, und
R⁴ und R⁵ stehen unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder bilden gemeinsam mit den Sauerstoffatomen, an die sie gebunden sind, und dem verbrückenden Kohlenstoffatom ein 5- oder 6-gliedriges gesättigtes Ringsystem, das gegebenenfalls mit einer C₁- bis C₄-Alkylgruppe substituiert sein kann,
mit der Maßgabe, dass mindestens einer der Reste R² oder R³ für einen Rest der Formel (II) steht.A first subject of the present invention are therefore p-phenylenediamine derivative of the formula I.

in which
R ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ alkoxy (C ₁ - to C ₄ ) alkyl group or a halogen atom and
R ² and R ³ independently of one another represent a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ Alkoxy (C ₁ to C ₄ ) alkyl group or a radical of the formula (II)

in which
X represents a C ₁ to C ₅ alkylene group which may optionally be substituted by a C ₁ to C ₄ alkyl group, a hydroxy group, a C ₁ to C ₄ alkoxy group or a halogen atom, and
R ⁴ and R ⁵ independently of one another represent a C ₁ - to C ₄ -alkyl group or together with the oxygen atoms to which they are attached and the bridging carbon atom form a 5- or 6-membered saturated ring system which may be linked with a C ₁ - to C ₄ alkyl group may be substituted,
with the proviso that at least one of the radicals R ² or R ^{3 represents} a radical of the formula (II).

Since it is in the p-phenylenediamine derivatives according to the invention about amino compounds acts, can be known from these in the usual way Acid addition salts produce. All statements in this document and accordingly the claimed The scope of protection therefore relate both to those in free form Compounds as well as their water-soluble, physiologically acceptable salts. Examples of such Salts are the hydrochlorides, the hydrobromides, the sulfates, the Phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred. The compounds according to the invention are very particularly preferably in free Shape.

Examples of the C ₁ to C ₄ alkyl groups 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 groups. Preferred C ₁ to C ₄ alkoxy groups are the methoxy and ethoxy groups. Further preferred examples of a C ₁ - to 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. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here.

According to the invention, p-phenylenediamine derivatives of the formula (I) in which R ^{1 represents} a hydrogen atom, a methyl group, a hydroxyethyl group or a chlorine atom are particularly preferred. The p-phenylenediamine derivatives in which R ^{1 represents} a hydrogen atom or a methyl group are very particularly preferred.

Furthermore, p-phenylenediamine derivatives of the formula (I) are preferred in which R ^{2 represents} a hydrogen atom, a β-hydroxyethyl group or a methyl group.

P-Phenylenediamine derivatives are also preferred of the formula (I) in which X is for is a methylene group or a propylene group.

Also preferred according to the invention are p-phenylenediamine derivatives of the formula (I) in which R ⁴ and R ⁵ independently of one another represent a methyl group or an ethyl group. P-Phenylenediamine derivatives in which R ⁴ and R ^{5 are} identical substituents are particularly preferred.

P-Phenylenediamine derivatives are very particularly preferred of formula (I) selected are composed of N- (2,2-dimethoxyethyl) -p-phenylenediamine, N- (4,4-dimethoxybutyl) -p-phenylenediamine, N- (2,2-diethoxyethyl) -p-phenylenediamine, N- (2,2-dimethoxyethyl) -N-methyl-p-phenylenediamine, N- (2,2-dimethoxyethyl) -3-methyl-p-phenylenediamine and N- (2,2-dimethoxyethyl) -N-methyl-3-methyl-p-phenylenediamine.

Leave the compounds of formula (I) yourself with the help of conventional produce organic methods. Here is an example on the experiments within the scope of the exemplary embodiments directed.

A second subject of the present Invention are coloring agents keratin fibers, especially human hair, in one at least cosmetically acceptable medium as developer component a p-phenylenediamine according to the invention of formula (I) included.

Among them are keratin fibers furs according to the invention, To understand wool, feathers and especially human hair. Even though the oxidation colorants of the invention primarily for dyeing of keratin fibers are suitable in principle for use also in other areas, especially in color photography, nothing against it.

In addition to the compounds of the invention of formula (I) the colorants contain one or more additional dye precursors.

• – Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, und
• – Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate, sowie Mischungen von Vertretern dieser Gruppen enthalten.

With regard to the further dye precursors which can be used in the colorants according to the invention, the present invention is not subject to any restrictions. The colorants according to the invention can be used as further dye precursors

• - Oxidation dye precursors of the developer and / or coupler type, and
• - Contain precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

In a first preferred embodiment contains the coloring agent at least one other developer component. As developer components are common primary aromatic amines with another, in para or ortho position located, free or substituted hydroxy or amino group, Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives as well as 2,4,5,6-tetraaminopyrimidine and its derivatives.

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

in which

• - G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy ( C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C _4- polyhydroxyalkyl, a C ₁ to C ₄ hydroxyalkoxy, a C ₁ to C ₄ acetylaminoalkoxy, a C ₁ to C ₄ mesylaminoalkoxy or a C ₁ to C ₄ carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• - 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 to C ₄ alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ to C ₄ hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms 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 the formula (E1) are in particular the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E 1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylene diamine, N, N-dimethyl-3-methyl-p-phenylene diamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylene diamine, 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 tolerable Salt.

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

It can continue according to the invention be preferred to use compounds as developer components, that contain at least two aromatic nuclei that are and / or hydroxyl groups are substituted.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, dass
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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:

• Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ to C ₄ alkyl radical, by a C ₁ to C ₄ hydroxyalkyl radical and / or by a bridging Y. is or is possibly part of a bridging ring system,
• - 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 and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to 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 - to C ₄ -alkyl radical, with the provisos that
• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of 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 analogous to the above explanations defined.

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis - ((β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylene diamine, Bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiological acceptable Salts.

Very particularly preferred dinuclear Developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis- (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of their physiological acceptable Salts.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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 C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy- (C ₁ - to C ₄ ) -alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ hydroxyalkyl aminoalkyl (C ₁ to C _4), or (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄₎ alkyl, and
• G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,
• G ¹⁵ represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ represents hydrogen or a halogen atom.

The substituents used in formula (E3) are analog according to the invention to the above statements Are defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol as well as their physiologically tolerable Salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino-2- (diethylaminomethyl) phenol.

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

Furthermore, the developer component selected be from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiological acceptable Salt.

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

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

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 are described, 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-l-methyl-3-phenylpyrazole, 4-amino-1,3 -dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl -3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- ( 4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4, 5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

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 there is a tautomeric equilibrium:

in which:

• - 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 has the value 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

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

• – Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazol-[1,5-a]-pynmidin-3,7-diamin;
• – 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can in particular mention nen:

• - pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 3-aminopyrazole- [1,5-a] pyrimidin-7-ol;
• - 3-aminopyrazole- [1,5-a] pyrimidin-5-ol;
• - 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;
• - 5,6-dimethylpyrazole- [1,5-a] -pynmidine-3,7-diamine;
• - 2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 3-amino-7-dimethylamino-2,5-dimethylpyrazole [1,5-a] pyrimidine;

as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

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

In a second preferred embodiment contain the colorants of the invention at least one coupler component.

As coupler components are in usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, Pyrazolone and m-aminophenol derivatives used. As coupler substances 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene are particularly suitable, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyrtdine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-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)-Benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino- 4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol.

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 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,
• 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, for example, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-amino-benzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

As precursors to natural dyes such indoles and indolines are preferably used, which at least a hydroxyl or amino group, preferably as a substituent on the six-membered ring, exhibit. These groups can carry further substituents, e.g. B. in the form of etherification or Esterification of the hydroxyl group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

in der unabhängig voneinanderDerivatives of 5,6-dihydroxyindoline of the formula (IIIa) are particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C 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 Indolins 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 as well as the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.

Of particular note are within this group N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5,6-dihydroxyindoline.

in der unabhängig voneinanderDerivatives of 5,6-dihydroxyindole of the formula (IIIb) are also outstandingly suitable as precursors of nature-analogous hair dyes,

in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C ₄ alkyl group, and
• R ⁵ stands for one of the groups mentioned under R ⁴ ,
• - such as physiologically acceptable Salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of Indoles 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.

To be highlighted within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5,6-dihydroxyindole.

The indoline and indole derivatives can in in the context of the inventive method colorants used both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. B. the hydrochloride, of sulfates and hydrobromides. The indole or Indoline derivatives are common in these in amounts of 0.05-10 % By weight, preferably 0.2-5 % By weight.

In another embodiment it can be preferred according to the invention be the indoline or Indole derivative in hair dye in combination with at least one amino acid or an oligopeptide use. The amino acid is advantageously an α-amino acid; all are particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

In addition to the p-phenylenediamine derivatives according to the invention of formula (I) can the colorants of the invention contain one or more substantive dyes for shading. Direct dyes are common 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, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 are known Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) 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 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 contain a cationic substantive dye. Especially are preferred

• (a) cationic triphenylmethane dyes, such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems with a quaternary nitrogen group are substituted, 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 which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in US Pat EP-A2-998 908 , to which reference is expressly made at this point, are mentioned in claims 6 to 11.

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

The compounds of the formulas (DZ1), (DZ3) and (DZS), which are also known as Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very special preferred cationic direct dyes of group (c).

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

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

The preparations according to the invention can also dyes occurring in nature, such as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, Sedre and alkanna root are included.

It is not required that the Oxidation dye precursors or the substantive dyes in each case represent uniform connections. Rather, in the hair colorants according to the invention, conditionally through the manufacturing processes for the individual dyes, additional components may be contained in minor quantities, as far as this is not the coloring result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding in the hair dyeing and -tönungsmitteln usable dyes will continue to expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive Dyes) and Chapter 8, pages 264-267; Oxidation dye precursors) published . as Volume 7 of the "Dermatology" series (Ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", published by the European Community, available in floppy form from the Federal Association of German Industry and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim, referred to.

The colorants according to the invention can all be used for such Contain preparations known active ingredients, additives and auxiliaries. In many cases contain the colorants at least one surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases However, it has proven to be advantageous to use anionic, select zwitterionic or nonionic surfactants.

Suitable anionic surfactants are in preparations according to the invention all for use on the human body suitable anionic surface-active Substances. These are characterized by a water-solubilizing, anionic group such as B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of about 10 up to 22 carbon atoms. additionally can in the molecule Glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups. Examples of suitable ones are anionic surfactants, each in the form of 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 -OOOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• - acyl sarcosides with 10 to 18 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 ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear Alkane sulfonates with 12 to 18 carbon atoms,
• - linear Alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl ester 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 C atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030 .
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354 .
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344 .
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide on fatty alcohols with 8 to 22 carbon atoms.

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

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

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 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well
• - Adducts 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 R ¹ O- (Z) _x . These connections are characterized by the following parameters.

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

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

• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• – im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen besteht.

Alkylpolyglycosides in which R ¹

• Essentially from C ₈ and C ₁₀ alkyl groups,
• Essentially from C ₁₂ and C ₁₄ alkyl groups,
• - essentially from C ₈ - to C ₁₆ alkyl groups or
• - consists essentially of C ₁₂ - to C ₁₆ alkyl groups.

Any sugar block Z can be used Mono- or oligosaccharides can be used. Usually sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Examples of such sugars are glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, Gulose, Idose, Talose and Sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Is glucose particularly preferred.

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

The alkyl glycosides can besides their surfactant effect also serve to fix fragrance components to improve on the hair. The specialist is therefore in the event that one over the effect of the perfume oil on the duration of the hair treatment the hair desired is preferred to this class of substances as a further ingredient of the preparations according to the invention To fall back on.

Even the alkoxylated homologues of the alkyl polyglycosides mentioned can be used according to the invention become. These homologues can on average up to 10 ethylene oxide and / or propylene oxide units included per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable nete zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2- Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. 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 ₁₈ -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. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

According to the invention as cationic surfactants in particular those of the quaternary ammonium compound type, the Esterquats and the Amidoamine used.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as Alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium 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 are preferred 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxy-ethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

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

Further usable according to the invention cationic surfactants are the quaternized protein hydrolyzates represents.

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".

For the compounds used as surfactants alkyl groups can be uniform substances act. However, it is usually preferred in manufacturing of these substances from native vegetable or animal raw materials to go out, so that you can mix substances with different depend on the respective raw material alkyl chain lengths receives.

In the case of surfactants, the add-on products of ethylene and / or propylene oxide to fatty alcohols or derivatives of these investment products, both products with a "normal" homolog distribution as well as those with a narrowed Homolog distribution can be used. Under "normal" homolog distribution are understood as mixtures of homologues that are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. On the other hand, narrow homolog distributions are obtained if, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallylammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylaminoethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazoliniummethochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylatltert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfiimöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-l-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Ölamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, (3-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, StyroUPVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien

enthalten.Furthermore, the colorants according to the invention can contain further active ingredients, auxiliaries and additives, such as, for example

• Non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - Cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidaternolino-copolymers,
• Zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl 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. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
• Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• - Quaternized amines such as methyl l-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers like silicones,
• Dyes for coloring the agent,
• - anti-dandruff agents such as piroctone oil amines, zinc omadine and climbazol,
• 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 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 the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, 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, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root.
• - cholesterol,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as walrus, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, (3-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, StyroUPVP and styrene / acrylamide copolymers
• Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - pigments,
• - stabilizing agents for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants

contain.

Regarding other optional Components as well as the amounts used of these components expressly to the relevant manuals known to those skilled in the art, e.g. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

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

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

The actual oxidative coloring of the Fibers can basically done with atmospheric oxygen. However, a chemical one is preferred Oxidizing agents are used, especially if, in addition to the coloring, a lightening effect wanted on human hair is. Persulfates, chlorites and in particular come as oxidizing agents Hydrogen peroxide or its adducts with urea, Melamine and sodium borate in question. According to the invention, however the oxidation colorant can also be applied to the hair together with a catalyst, which the oxidation of the dye precursors, e.g. through atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , C ²⁺ , Fe ²⁺ , Fe ²⁺ , Mn ²⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al3 ⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

 Suitable enzymes are e.g. peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Farther are such enzymes suitable according to the invention, with the help of atmospheric oxygen the oxidation dye precursors oxidize directly, such as laccases, or in situ generate small amounts of hydrogen peroxide and in this way the Activate oxidation of the dye precursors biocatalytically. Especially suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with those for it specific substrates, e.g.

• - pyranose oxidase and e.g. D-glucose or galactose,
• - glucose oxidase and D-glucose,
• - glycerin oxidase and glycerin,
• - pyruvate oxidase and pyruvic acid or their salts,
• - alcohol oxidase and alcohol (MeOH, EtOH),
• - lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• - uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

The actual hair dye will be convenient immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the dye precursors, manufactured. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Especially preference is given to using the hair dye in a weakly alkaline Milieu. The application temperatures can range between 15 and 40 ° C lie. After an exposure time of 5 to 45 minutes, it will Hair Dye by rinsing of the one to be colored Hair removed. Washing with a shampoo is not necessary if a high tenside carrier, e.g. a coloring shampoo, was used.

Especially when it is difficult to color Hair can also be prepared with the dye precursors without prior mixing with the oxidation component on the Hair are applied. After an exposure time of 20 to 30 minutes then - if necessary after an intermediate rinse - the oxidation component applied. After a further exposure time of 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to one first variant, in which the previous rising of the dye precursors a better penetration into the hair is supposed to effect the corresponding Means adjusted to a pH of about 4 to 7. According to one the second variant is first a Air oxidation sought, with the applied agent preferred has a pH of 7 to 10. At the subsequent accelerated Postoxidation can be the use of acidified peroxidisulfate solutions as Oxidizing agents may be preferred.

A third subject of the present Registration is the use of the p-phenylediamine derivatives according to the invention for coloring keratin fibers.

A fourth subject of the present Invention is a process for coloring keratin fibers, in which a hair dye according to the invention is applied to the fibers and is rinsed off after an exposure time.

According to the invention, it can be special be preferred, the fibers immediately after the actual coloring with an acidic aqueous flush to treat. Without this embodiment restrict in any way wanting, it is based on the following model: the acidic aftertreatment could cause hydrolysis of the acetal functions. The freed up by it Aldehyde functions could then bind to the protein structure of the hair and in this way improve the fastness properties of the dyeing obtained.

wobei
R¹ steht für ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe, eine C₁- bis C₄-Monohydroxyalkylgruppe, eine C₂- bis C₄- Polyhydroxyalkylgruppe, eine C₁- bis C₄-Alkoxy-(C₁- bis C₄)-alkylgruppe oder ein Halogenatom und
R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe, eine C₁- bis C₄-Monohydroxyalkylgruppe, eine C₂- bis C₄-Polyhydroxyalkylgruppe, eine C₁- bis C₄-Alkoxy-(C₁- bis C₄)-alkylgruppe oder einen Rest der Formel (II)

wobei
X steht für eine C₁- bis C₅-Alkylengruppe, die gegebenenfalls mit einer C₁- bis C₄-Alkylgruppe, einer Hydroxygruppe, einer C₁- bis C₄-Alkoxygruppe oder einem Halogenatom substituiert sein kann, und
R⁴ und R⁵ stehen unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder bilden gemeinsam mit den Sauerstoffatomen, an die sie gebunden sind, und dem verbrückenden Kohlenstoffatom ein 5- oder 6-gliedriges gesättigtes Ringsystem, das gegebenenfalls mit einer C₁- bis C₄-Alkylgruppe substituiert sein kann,
mit den Maßgaben, dassA fifth object of the present invention are 4-nitroanilines of the formula (I ')

in which
R ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ alkoxy (C ₁ - to C ₄ ) alkyl group or a halogen atom and
R ² and R ³ independently of one another represent a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ Alkoxy (C ₁ to C ₄ ) alkyl group or a radical of the formula (II)

in which
X represents a C ₁ to C ₅ alkylene group which may optionally be substituted by a C ₁ to C ₄ alkyl group, a hydroxy group, a C ₁ to C ₄ alkoxy group or a halogen atom, and
R ⁴ and R ⁵ independently of one another represent a C ₁ - to C ₄ -alkyl group or together with the oxygen atoms to which they are attached and the bridging carbon atom form a 5- or 6-membered saturated ring system which may be linked with a C ₁ - to C ₄ alkyl group may be substituted,
with the proviso that

• - At least one of the radicals R ² or R ^{3 represents} a radical of the formula (II) and
• - If R ¹ and R ^{2 are} hydrogen and X is a methylene group, then R ⁴ and R ⁵ do not simultaneously represent methyl groups.

Particularly preferred 4-nitroanilines of the formula (I ') are N- (4,4-dimethoxybutyl) -4-nitroaniline, N- (2,2-diethoxyethyl) -4-nitroaniline, N- (2,2-dimethoxyethyl) -N-methyl-4-nitroaniline, N- (2,2-dimethoxyethyl) -3-methyl-4-nitroaniline and N- (2,2-dimethoxyethyl) -N-methyl-3-methyl-4-nitroaniline.

1. Synthesis 1.1. N- (2,2-dimethoxyethyl) -p-phenylenediamine

1.1.1. N- (2,2-dimethoxyethyl) -4-nitro-aniline

150 ml of DMSO were placed in a 500 ml three-necked flask and mixed with 22.6 g of triethanolamine (99%), 47.7 g of aminoacetaldehyde dimethyl acetal (99%) and 21.8 g of 1-fluoro-4-nitrobenzene (97%) added. The mixture was stirred at 80 ° C for 19.5 h. The mixture was then cooled to room temperature and poured onto 1.5 l of ice. The resulting precipitate was filtered off and dried in vacuo at 50 ° C.
Yield: 34.2 g (100%)
Melting point: 70-72 ° C

1.1.2. N- (2,2-dimethoxyethyl) -p-phenylenediamine

22.6 g of N- (2,2-dimethoxyethyl) -4-nitro-aniline were dissolved in 400 ml of methanol, mixed with 0.4 g of Pd / C (5%) and in a hydrogen shaker at room temperature and normal pressure catalytically reduced. When the uptake of hydrogen had ended, the mixture was filtered and concentrated to dryness in vacuo. The red oil thus obtained was then distilled in a bulb tube (0.8 mbar, 162-180 ° C).
Yield: 15.2 g (77%) 1.2. N- (4,4-dimethoxybutyl) -p-phenylenediamine

1.2.1. N- (4,4-dimethoxybutyl) -4-nitro-aniline

150 ml of DMSO were placed in a 500 ml three-necked flask, and 22.6 g of triethanolamine (99%), 50 g of 4-aminobutyraldehyde dimethyl acetal and 21.8 g of 1-fluoro-4-nitrobenzene (97%) were added. The mixture was stirred at 80 ° C for 17.5 h. The mixture was then allowed to cool to room temperature and poured onto 1 l of ice, a yellow oil precipitating out, which crystallized after about 1 h. The resulting precipitate was filtered off, washed with water and dried in vacuo at 40 ° C.
Yield: 38 g (100%)
Melting point: 69-70 ° C

1.2.2. N- (4,4-dimethoxybutyl) -p-phenylenediamine

35.6 g of N- (4,4-dimethoxybutyl) -4-nitro-aniline were dissolved in 400 ml of methanol, mixed with 1 g Pd / C (5%) and in a hydrogen shaker catalytically reduced at room temperature and normal pressure. After finished Hydrogen uptake was filtered and in vacuo to dryness concentrated. The red oil thus obtained was then in the Kugelrohr distilled (0.1 mbar, 240-250 ° C).

Yield: 27.8 g (88%) 1.3. N- (2,2-diethoxyethyl) -p-phenylenediamine

1.3.1. N- (2,2-diethoxyethyl) -4-nitro-aniline

150 ml of DMSO were placed in a 500 ml three-necked flask, and 22.6 g of triethanolamine (99%), 50 g of aminoacetaldehyde diethylacetal (98%) and 21.8 g of 1-fluoro-4-nitrobenzene (97%) were added. The mixture was stirred at 80 ° C for 10 h. The mixture was then allowed to cool to room temperature and poured onto 1 l of ice, a yellow oil precipitating out, which crystallized after about 1 h. The resulting precipitate was filtered off, washed with water and dried in vacuo at 30 ° C.
Yield: 38 g (100%)
Melting point: 49-52 ° C

1.3.2. N- (2,2-diethoxyethyl) -p-phenylenediamine

35.6 g of N- (2,2-diethoxyetyl) -4-nitro-aniline were dissolved in 400 ml of ethanol, 1 g of Pd / C (5%) was added and the mixture was reduced catalytically in a hydrogen shaker at room temperature and normal pressure , When the uptake of hydrogen had ended, the mixture was filtered and concentrated to dryness in vacuo. The red oil thus obtained was then distilled in a bulb tube (0.12 mbar, 230 ° C).
Yield: 27.9 g (88%) 1.4. N- (2,2-dimethoxyethyl) -N-methyl-p-phenylenediamine

1.4.1. N- (2,2-dimethoxyethyl) -N-methyl-4-nitro-aniline

250 ml of DMSO are placed in a 1000 ml three-necked flask and mixed with 45.2 g of triethanolamine (99%), 98.3 g of N-methylaminoacetaldehyde dimethyl acetal (97%) and 42.3 g of 1-fluoro-4-nitrobenzene (97% ig) offset. The mixture was stirred at 80 ° C for 19 h. The mixture was then allowed to cool to room temperature and poured onto 1 liter of ice, a yellow oil precipitating out.
Yield: 71 g (98%)

1.4.2. N- (2,2-dimethoxyethyl) -N-methyl-p-phenylenediamine

66.1 g of N- (2,2-dimethoxyethyl) -N-methyl-4-nitro-aniline were dissolved in 400 ml of methanol, 1 g of Pd / C (5%) was added and in a hydrogen shaker at room temperature and normal pressure catalytically reduced. When the uptake of hydrogen had ended, the mixture was filtered and evaporated to dryness in vacuo. The red oil thus obtained was then distilled in a bulb tube (0.16 mbar, 190 ° C).
Yield: 39.9 g (69%) 1.5. N- (2,2-dimethoxyethyl) -3-methyl-p-phenylenediamine

1.5.1. N- (2,2-dimethoxyethyl) -3-methyl-4-nitro-aniline

150 ml of DMSO were placed in a 500 ml three-necked flask and mixed with 22.6 g of triethanolamine (99%), 47.8 g of aminoacetaldehyde dimethyl acetal (99%) and 24.0 g of 1-fluoro-3-methyl-4-nitrobenzene ( 97%) offset. The mixture was stirred at 80 ° C for 20 h. The mixture was then allowed to cool to room temperature and poured onto 1 l of ice, a yellow oil precipitating out, which crystallized after about 1 h. The resulting precipitate was filtered off, washed with water and dried in vacuo at 50 ° C.
Yield: 36 g (100%)
Melting point: 68-70 ° C

1.5.2. N- (2,2-dimethoxyethyl) -3-methyl-p-phenylenediamine

33.6 g of N- (2,2-dimethoxyethyl) -3-methyl-4-nitroaniline were dissolved in 400 ml of methanol, mixed with 1.2 g of Pd / C (5%) and in a hydrogen shaker at room temperature and normal pressure catalytically reduced. When the uptake of hydrogen had ended, the mixture was filtered and concentrated to dryness in vacuo. The red oil thus obtained was then distilled in a bulb tube (0.12 mbar, 225 ° C).
Yield: 23.6 g (80%) 1.6. N- (2,2-dimethoxyethyl) -N-methyl-3-methyl-p-phenylenediamine

1.6.1. N- (2,2-dimethoxyethyl) -N-methyl-3-methyl-4-nitro-aniline

150 ml of DMSO were placed in a 500 ml three-necked flask and mixed with 22.6 g of triethanolamine (99%), 47.8 g of methylaminoacetaldehyde dimethyl acetal (99%) and 24 g of 1-fluoro-3-methyl-4-nitrobenzene (97% ig) offset. The mixture was stirred at 80 ° C for 19 h. The mixture was then allowed to cool to room temperature and poured onto 1 l of ice, a yellow oil precipitating out, which crystallized after about 1 h. The resulting precipitate was filtered off, washed with water and dried in vacuo at 35 ° C.
Yield: 38 g (100%)
Melting point: 56-59 ° C

1.6.2. N- (2,2-dimethoxyethyl) -N-methyl-3-methyl-p-phenylenediamine

35.6 g of N- (2,2-dimethoxyethyl) -N-methyl-3-methyl-4-nitroaniline were dissolved in 400 ml of methanol, mixed with 0.5 g of Pd / C (5%) and in a hydrogen - Shaking apparatus catalytically reduced at room temperature and normal pressure. When the uptake of hydrogen had ended, the mixture was filtered and concentrated to dryness in vacuo. The red oil thus obtained was then distilled in a bulb tube (0.16 mbar, 190-225 ° C).
Yield: 25.2 g (80%)

2. Discolorations

2.1. Experimental Procedure

For the production of the coloring cream, 50 g of a cream base were weighed into a 250 ml beaker and melted at 80 ° C. The cream base used had the following composition:

1/400 mol of the developer or coupler component separately suspended in distilled water or while heating solved. Subsequently ammonia (<1 ml; 25% ammonia solution) added until the pH was between 9 and 10. By adding ammonia a solution was created.

The dissolved dye precursors were one after the other in the hot Cream incorporated. Subsequently was made up to 97 g with distilled water and a pH value with ammonia set from 9.5. After filling up the batch was cold stirred with distilled water to 100 g (<30 ° C.), whereby a homogeneous cream was created.

For the coloring, 25 g of coloring cream were mixed with 25 g of an aqueous 3% by weight H ₂ O ₂ solution.

A strand of hair (80% gray; 330 mg to 370 mg in weight) was added to each of the mixtures thus obtained. The mixtures and the strands of hair were then each placed on a watch glass and the strands of hair were well embedded in the coloring creams. After 30 minutes (± 1 minute) of exposure at room temperature, the strands of hair were removed and with an aqueous Texapon ^® EVR solution washed until the excess paint was removed. The strands of hair were air-dried and their shade determined and noted under the daylight lamp (color testing device HE240A) (Taschenlexikon der Farben, A. Kornerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag; Zurich, Göttingen).

2.3. Ausfärbungen mit N-(4,4-Dimethoxybutyl)-p-phenylendiamin

2.4. Ausfärbungen mit N-(2,2-Diethoxyethyl)-p-phenylendiamin

2.5. Ausfärbungen mit N-(2,2-Dimethoxyethyl)-N-methyl-p-phenylendiamin

2.6. Ausfärbungen mit N-(2,2-Dimethoxyethyl)-3-methyl-p-phenylendiamin

2.7. Ausfärbungen mit N-(2,2-Dimethoxyethyl)-N-methyl-3-methyl-p-phenylendiamin

The results obtained in the coloration tests are shown in the tables below. 2.2. Colorings with N- (2,2-dimethoxyethyl) -p-phenylenediamine

2.3. Colorings with N- (4,4-dimethoxybutyl) -p-phenylenediamine

2.4. Colorings with N- (2,2-diethoxyethyl) -p-phenylenediamine

2.5. Colorings with N- (2,2-dimethoxyethyl) -N-methyl-p-phenylenediamine

2.6. Colorings with N- (2,2-dimethoxyethyl) -3-methyl-p-phenylenediamine

2.7. Colorings with N- (2,2-dimethoxyethyl) -N-methyl-3-methyl-p-phenylenediamine

Claims (12)

p-phenylenediamine derivative of the formula (I)

where R ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ alkoxy (C ₁ - to C ₄ ) -alkyl group or a halogen atom and R ² and R ³ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl group, a C ₁ - to C ₄ -monohydroxyalkyl group, a C ₂ - to C ₄ -polyhydroxyalkyl group, a C ₁ - to C ₄ -alkoxy- (C ₁ - to C ₄ ) -alkyl group or a radical of the formula (II)

where X stands for a C ₁ - to C ₅ -alkylene group, which may optionally be substituted with a C ₁ - to C ₄ -alkyl group, a hydroxy group, a C ₁ - to C ₄ -alkoxy group or a halogen atom, and R ⁴ and R ⁵ independently of one another represent a C ₁ - to C ₄ -alkyl group or together with the oxygen atoms to which they are attached and the bridging carbon atom form a 5- or 6-membered saturated ring system which, if appropriate, with a C ₁ - bis C ₄ alkyl group can be substituted, with the proviso that at least one of the radicals R ² or R ^{3 represents} a radical of the formula (II). p-Phenylenediamine derivative according to claim 1, characterized in that R ¹ represents a hydrogen atom, a methyl group, a hydroxyethyl group or a chlorine atom. p-Phenylenediamine derivative according to claim 2, characterized in that R ¹ represents a hydrogen atom or a methyl group. p-Phenylenediamine derivative according to any one of claims 1 to 3, characterized in that R ² represents a hydrogen atom, a β-hydroxyethyl group or a methyl group. p-phenylenediamine derivative according to one of claims 1 to 4, characterized in that that X stands for one Methylene group or a propylene group. p-Phenylenediamine derivative according to one of claims 1 to 5, characterized in that R ⁴ and R ⁵ independently of one another represent a methyl group or an ethyl group. p-Phenylenediamine derivative according to one of claims 1 to 6, characterized in that R ⁴ and R ^{5 are} identical. p-phenylenediamine derivative according to one of claims 1 to 7, characterized in that that it is selected is from N- (2 ', 2'-dimethoxyethyl) -p-phenylenediamine, N- (4', 4'-dimethoxyeutyl) -p-phenylenediamine, N- (2 ', 2'-diethoxyethyl) -p-phenylenediamine, N- (2 ', 2'-dimethoxyethyl) -N-methyl-p-phenylenediamine, N- (2', 2'-dimethoxyethyl) -3-methyl-p-phenylenediamine and N- (2 ', 2'-dimethoxyethyl) -N-methyl-3-methyl-p-phenylenediamine. Colorants keratin fibers, especially human hair, characterized in that it in a cosmetically acceptable medium as a developer component at least one p-phenylenediamine according to any one of claims 1 to 8 contains. Coloring process keratin fibers, characterized in that an agent after Claim 9 is applied to the fibers and after an exposure time rinsed off again becomes. A method according to claim 10, characterized in that the Fibers afterwards with an acidic aqueous flush be treated. 4-nitroaniline derivative of the formula (I ')

where R ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₁ to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a C ₁ to C ₄ alkoxy (C ₁ - to C ₄ ) -alkyl group or a halogen atom and R ² and R ³ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl group, a C ₁ - to C ₄ -monohydroxyalkyl group, a C ₂ - to C ₄ -polyhydroxyalkyl group, a C ₁ - to C ₄ -alkoxy- (C ₁ - to C ₄ ) -alkyl group or a radical of the formula (II)

where X stands for a C ₁ - to C ₅ -alkylene group, which may optionally be substituted with a C ₁ - to C ₄ -alkyl group, a hydroxy group, a C ₁ - to C ₄ -alkoxy group or a halogen atom, and R ⁴ and R ⁵ independently of one another represent a C ₁ - to C ₄ -alkyl group or together with the oxygen atoms to which they are attached and the bridging carbon atom form a 5- or 6-membered saturated ring system which, if appropriate, with a C ₁ - bis C ₄ alkyl group can be substituted, with the provisos that - at least one of the radicals R ² or R ^{3 represents} a radical of the formula (II) and - if R ¹ and R ^{2 represent} hydrogen and X is a methylene group, then R ⁴ and R ⁵ do not simultaneously represent methyl groups.