DE102004039357A1 - Oxidation colorant with Diaminobenzolderivaten - Google Patents

Abstract

The present invention relates to oxidation colorants for dyeing keratin fibers, in particular human hair, containing at least one coupler component and at least one developer component in a water-containing carrier, wherein the coupler component is selected from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted Pyridine derivatives and the developer component is selected from the compounds according to formula (I), DOLLAR F1 in the R1 and R2 independently of one another for a hydrogen atom, a linear or cyclic C¶1¶-C¶6¶-alkyl group, a C¶2¶- C¶6¶ alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a C¶1¶-C¶6¶-hydroxyalkyl group, a C¶2¶-C¶6¶-polyhydroxyalkyl group, a C ¶1¶-C¶6¶ alkoxy-C¶2¶-C¶6¶ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group stand in which the radicals R 1 and R 2 may together form a saturated ring which may contain further heteroatoms, such as N or O, and the radical R 3 is a hydrogen atom, a halogen atom, a C 2-10 alkyl group, a C ¶1¶-C¶6¶-hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C¶1¶-C¶6¶-alkoxy group, a nitro group, a hydroxy-C¶1¶-C¶6¶-alkoxy group , a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in which n is 3,4 or 5,

Description

The Invention relates to dyeing agents of keratin fibers containing special diaminobenzene derivatives as a developer component contain in combination with at least one coupler component, a method of dyeing of keratin fibers with these agents, as well as the use of the dye combinations of the invention in cosmetic centers, in particular for dyeing keratin fibers.

Under Keratin fibers are inventively furs, wool, feathers and especially the human hair understood. The human hair is becoming more diverse today Treated with hair cosmetic preparations. These include about The cleansing of hair with shampoos, the care and regeneration with rinses and cures, as well as bleaching, dyeing and deforming the hair with colorants, Tints, Wells and styling preparations. There are funds for change or nuancing the color of the head hair a prominent role.

For temporary dyeings become common dyeing or tinting agent used as dyeing Component so-called direct pullers included. This is it about dye molecules, which grow directly on the hair and no oxidative process to training need the color. Belongs to these dyes for example, that from ancient times to the coloring of body and hairs known henna. These dyes are against shampooing usually sensitive, so that one often unwanted Shade shift or even a visible "discoloration" may occur.

For dyeing Keratin fibers, especially hair, play the so-called An oxidation because of their intense colors and good fastness properties, at a relatively low dyeing temperature and in short dyeing times achieved a special role. Such colorants contain in a suitable, usually aqueous carrier one Developer component, which under the influence of atmospheric oxygen or of Oxidants by oxidative coupling forms the dye. This dye can be made by coupling with another developer component or with so-called coupler components which themselves are not dyes can train intensified and modified in nuance.

Quality Oxidation dye precursors are primarily intended to meet the following requirements fulfill: You need to in the oxidative coupling the desired color shades in sufficient intensity and train authenticity. You need to Furthermore, a good Aufziehvermögen to possess the fiber, in particular in human hair no noticeable differences between strained and fresh allowed to exist after hair regrowth (Leveling). They should be consistent be against light, heat, Friction and the influence of chemical Reducing agents, e.g. Perm liquids. Finally, should if they are as hair dye coming to the application - the Do not stain the scalp too much, and above all, they should be toxicological and dermatological Regard safe. Furthermore, the color obtained by Bleaching can be easily removed from the hair if they do not meet the individual wishes of the individual person corresponds and reversed shall be.

For hair dyeing and tint In particular, the color nuances in the red and brown areas is of considerable importance too, as they are natural for generating acting hair dyeings are mandatory. Oxidation dyes in red and brown, as they are e.g. with the combination of 2,4,5,6-tetraaminopyrimidine and 2-methylresorcinol accessible are not yet optimal in terms of uniformity of the color elevator. Direct dyes are usually less washfast and therefore not so good for combination with oxidation dyes suitable.

Out these reasons there is a need for novel oxidation dye precursors, which allow an improvement of the above parameters. Surprisingly it was found that certain Diaminobenzolerivate the above requirements in excellent Way.

• – die Kupplerkomponente ausgewählt ist aus m-Phenylendiaminderivaten, Naphtholen, Resorcin und Resorcinderivaten, Pyrazolonen, m-Aminophenolen und substituierten Pyridinderivaten und
• – die Entwicklerkomponente ausgewählt ist aus den Verbindungen gemäß Formel (I),
  

in der R1 und R2 unabhängig voneinander für ein Wasserstoffatom, eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine substituierte oder unsubstituierte Arylgruppe, eine substituierte oder unsubstituierte Heteroarylgruppe, eine Arylalkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine Aminoalkylgruppe, eine Dialkylaminoalkylgruppe stehen, wobei die Reste R1 und R2 gemeinsam einen gesättigten Ring bilden können, der weitere Heteroatome wie N oder O enthalten kann und der Rest R3 für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine Hydroxygruppe, eine Aminogruppe, eine Dialkylaminogruppe, eine C₁-C₆-Alkoxygruppe, eine Nitrogruppe, eine Hydroxy-C₁-C₆-alkoxygruppe, eine Carboxygruppe, eine Sulfonylgruppe, eine Sulfonamidogruppe oder eine Carboxamidogruppe stehen und in der n für 3, 4 oder 5 steht, sowie deren Salzen mit einer anorganischen oder organischen Säure.A first subject of the invention is therefore an oxidation dye for dyeing keratin fibers, in particular human hair, comprising at least one coupler component and at least one developer component in a water-containing carrier, wherein

• The coupler component is selected from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives and
• The developer component is selected from the compounds according to formula (I),
  

in the R _{1 and} R ₂ independently of one another represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, wherein the radicals R _{1 and} R ₂ together form a saturated ring which may contain further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ alkoxy group, a nitro group, a hydroxy-C ₁ -C ₆ alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in which n is 3, 4 or 5, and de salts with an inorganic or organic acid.

Examples of C ₁ -C ₆ -alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C ₂ -C ₆ alkenyl groups are vinyl, allyl and butenyl, with vinyl and allyl being particularly preferred. Preferred C ₁ -C ₆ -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 ₆ 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. As hydrochlorides, sulfates or hydrobromides understood.

In a preferred embodiment in the present invention, n is as shown above Formula (I) for 3 or 4. Preferred agents according to the invention are therefore characterized characterized in that they a developer component of the formula (I) in which n is 3 or 4 stands.

In a further preferred embodiment In the present invention, the radicals R1, R2 and R3 in the represented above formula (I) for a hydrogen atom. Especially preferred agents according to the invention are characterized in that they a developer component of the formula (I) in which the radicals R1, R2 and R3 for represent a hydrogen atom.

Especially preferred oxidation colorants according to the invention are characterized in that the Compound according to formula (I) selected is from 4-amino-5,6,7,8-tetrahydro-1-naphthylamine and / or 7-amino-2,3-dihydro-1H-inden-4-ylamine.

The agents according to the invention contain the compounds according to formula (I) preferably in an amount of 0.01 to 20 wt .-%, based on the entire colorant.

• [1] Bamberger; Schieffelin; CHBEAM; Chem.Ber. 1889; 22; 1376.
• [2] Schroeter; JLACBF; Justus Liebigs Ann. Chem. 1922; 426; 132.
• [3] Micklethwait; Winfield; JCSOA9; J.Chem.Soc. 1904; 85; 751
• [4] Green; Rowe; JCSOA9; J.Chem.Soc. 1918; 113;; 968.

bekannten Wege zurückgegriffen werden.The diaminobenzene derivatives of the formula I are prepared by known processes of organic synthesis. For example, for the synthesis of 4-amino-5,6,7,8-tetrahydro-1-naphthylamine, for example, on the

• Bamberger; Schieffelin; CHBEAM; Ber. 1889; 22; 1376th
• [2] Schroeter; JLACBF; Justus Liebigs Ann Chem. 1922; 426; 132nd
• [3] Micklethwait; Winfield; JCSOA9; J. Chem. 1904; 85; 751
• [4] Green; Rowe; JCSOA9; J. Chem. 1918; 113 ;; 968th

recourse to known ways.

In addition to the diaminobenzene derivatives according to the invention, the agents according to the invention contain white terhin at least one coupler component from the group of m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. These will be described below.

• 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-Trifluoracetylamino-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, 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-Aminobenzomorpholin,
• – 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,

According to preferred coupler components 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, 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-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• Methylene dioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene,

Especially 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-methylphenol, 2-methylresorcinol, 2- (2 ', 4'-diaminophenoxy) ethanol, 1,3-bis (2 ', 4'-diamino-phenoxy) propane; Resorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, m-aminophenol, 1,7-, 2,7- and 1,5-dihydroxynaphthalene as well as 4-hydroxyindole and 6-hydroxyindole.

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

3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin

2-[(3-Morpholin-4-ylphenyl)amino]ethanol dihydrochlorid

Further preferred coupler components are 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol

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

3-Amino-4- (2-methoxyethoxy) -5-methylphenylamine

2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol dihydrochloride

In summary are oxidation colorants according to the invention preferred in which the coupler component is selected from resorcinol, 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1,3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 4-chlororesorcinol 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, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino ) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-Amino-4- (2-methoxyethoxy) -5-methylphenylamine and 2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol dihydrochloride.

The oxidation colorants according to the invention contain the coupler component (s) preferably in an amount of 0.01 to 20% by weight, preferably from 0.5 to 5% by weight, and the developer component (s) in an amount of 0.01 to 20% by weight, preferably 0.5 to 5 wt .-%, each based on the total oxidation colorant.

there become developer components and coupler components in general used in about molar amounts to each other. If also the molar use proved to be useful has, so is a certain excess of individual Oxidation dye precursors not disadvantageous, so that developer components and Coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, may be included.

preferred Oxidation colorants of the invention are characterized in that they in addition to the coupler components from the group of m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives and the compounds according to formula (I) contain no further oxidation dye precursors.

Only with a developer component or a special coupler / developer combination succeeds usually not to get a natural color on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye combinations. Therefore, other preferred oxidation hair colorants may contain other developer components in addition to the compounds of formula (I).

When other developer components are usually primary aromatic Amines with another, in 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 used its derivatives.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen (C₁-C₄)-Alkoxy-(C₁-C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁-C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist,
• – G² steht für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen (C₁-C₄)-Alkoxy-(C₁-C₄)-alkylrest oder einen C₁-C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist,
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Hydroxyalkoxyrest, einen C₁-C₄-Acetylaminoalkoxyrest, einen C₁-C₄-Mesylaminoalkoxyrest oder einen C₁-C₄-Carbamoylaminoalkoxyrest,
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁-C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise einen Ethylendioxygruppe bilden.

It may be preferred according to the invention to use as additional 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 radical, a 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 -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a (C ₁ -C ₄ ) -alkoxy- (C ₁ - C ₄ ) -alkyl radical 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 -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl 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 the formula (II) are, in particular, the amino groups, C ₁ -C ₄ -monoalkylamino groups, C ₁ -C ₄ -dialkylamino groups, C ₁ -C ₄ -trialkylammonium groups, C ₁ -C ₄ -monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (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-hydro xyethyloxy) -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 particular according to the invention preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

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

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, das gegebenenfalls durch einen C₁-C₄-Alkylrest, durch einen C₁-C₄-Monohydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder das 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-C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁-C₄-Alkylrest, einen C₁-C₄-Monohydroxyalkylrest, einen C₂-C₄- Polyhydroxyalkylrest, einen C₁-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-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 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, 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 -hydroxyalkyl radical, a C ₁ -C ₄ - Aminoalkyl radical or a direct compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently 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 used in formula (E2) substituents are analogous to the invention to the above statements Are defined.

preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diaminopropane-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-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-aminophenyl) diaza-cycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically tolerable 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-te traoxadecane or one of its physiologically acceptable salts.

wobei

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

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 radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a (C ₁ -C ₄ ) -alkoxy radical 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 is a hydrogen or halogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -hydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a (C ₁ -C ₄ ) -alkoxy radical C ₁ -C ₄ ) -alkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a C ₁ -C ₄ -cyanoalkyl radical,
• G ¹⁵ is hydrogen, a C ₁ -C ₄ -alkyl radical, a 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 used in formula (E3) substituents are analogous 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-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 as well as their physiologically tolerable Salts.

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

Further can the extra Developer component selected be from o-aminophenol and its derivatives such as 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

Farther can the extra Developer component selected be heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salts: Preferred according to the invention are pyrimidine or pyrazole derivatives.

preferred Pyrimidine derivatives are in particular the compounds 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 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-hydrazinopyrazol, 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-hydroxymethyl-, 4,5-Diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-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 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diaminopyridine.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen Aryl-Rest, einen C₁-C₄-Hydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest einen (C₁-C₄)-Alkoxy-(C₁-C₄)-alkylrest, einen C₁-C₄-Aminoalkylrest, das gegebenenfalls durch einen Acetyl-Ureid- oder Sulfonyl-Rest geschützt sein kann, einen (C₁-C₄)-Alkylamino-(C₁-C₄)-alkylrest, einen Di-[(C₁-C₄)-alkyl]-(C₁-C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁-C₄-Hydroxyalkyl- oder einen Di-(C₁-C₄)-[Hydroxyalkyl]-(C₁-C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁-C₄-Alkylrest, einen Aryl-Rest, einen C₁-C₄-Hydroxyalkylrest, einen C₂-C₄-Polyhydroxyalkylrest, einen C₁-C₄-Aminoalkylrest, einen (C₁-C₄)-Alkylamino-(C₁-C₄)-alkylrest, einen Di-[(C₁-C₄)alkyl]-(C₁-C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁-C₄-Hydroxyalkyl- oder einen Di-(C₁-C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁-C₄-Alkyl- oder Di-(C₁-C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, daß
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent 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 ) -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, a di - [(C ₁ -C ₄ ) alkyl] (C ₁ -C ₄ ) aminoalkyl, wherein the dialkyl radicals optionally have one 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] - (C ₁ -C ₄ ) -aminoalkyl radical,
• - The X radicals independently of one another represent 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 with 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 radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• The sum of p + q is not equal to 0,
• If p + q 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 used in formula (E4) substituents are analogous to the invention to the above statements Are 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:

• – 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-Amino pyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Amino pyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Amino pyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Amino pyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Amino pyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Amino pyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,6-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5, N7, N7-Tetramethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomeres Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4):

• - pyrazolo [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 Pyrazole- [1,5-a] -pyrimidines of the above formula (E4) can, as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

According to the invention preferred additional Developer components are pyrimidine derivatives, pyrazole derivatives, p-aminophenol derivatives and p-phenylenediamine derivatives.

Especially preferred additional 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.

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

Another preferred additional developer component is N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine trihydrochloride):

In summary are oxidation colorants according to the invention preferred, which contain a further developer component, the selected is from 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-diaminophenoxy) -ethanol, N, N-bis (2'-hydroxyethyl) -1,4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 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-tetraoxadecan, 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, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole and N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine trihydrochloride.

Farther can the agents according to the invention Precursors of natural analog dyes included. As precursors of natural analogue Dyes are preferably used such indoles and indolines, the at least one hydroxy or amino group, preferably as a substituent at the six-ring, exhibit. These groups may have additional substituents wear, z. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.

in der unabhängig voneinander
R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
R⁵ steht für eine der unter R⁴ genannten Gruppen,
sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIa),

in the independently of each other
R ¹ is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkenyl or C ₁ -C ₄ hydroxyalkyl,
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.

Especially preferred derivatives of indoline are the 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Especially 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.

in der unabhängig voneinander
R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe, eine C₃-C₆-Cycloalkylgruppe, eine C₂-C₄-Alkenylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
R⁵ steht für eine der unter R⁴ genannten Gruppen,
sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.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 is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkenyl or C ₁ -C ₄ hydroxyalkyl,
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.

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

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

The indoline and indole derivatives can be used in the inventive colorants 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 are used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

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

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

Substantive Dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are the 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 Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Appropriate inventive agent, which are characterized in that they at least one substantive Dye included, selected is from nitrophenylenediamines, nitroaminophenols, azo dyes, Anthraquinones or indophenols, preferably from the group of known under international names or trade names Dyes HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro 2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic and their salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene are preferred.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterozyklus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

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

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, which is incorporated herein by reference, in claims 6 to 11.

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

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive Dyes of group (c).

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

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

Farther can the preparations according to the invention also occurring in nature dyes such as, for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alkano root are included.

It it is not necessary that the oxidation dye precursors or the direct dyes in each case uniform compounds represent. Rather, you can in the hair colorants according to the invention by the manufacturing processes for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding the in the hair dyeing and -tönungsmitteln applicable dyes is still expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; Dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology" (ed. Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", issued by the European Community, available in diskette form from the German Association of Industrial and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim.

In a further embodiment, the agent according to the invention additionally contains a combination of component
A compounds containing a reactive carbonyl group with component
B Compounds selected from (a) CH-acidic compounds, (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) from 2 up to 9 amino acids oligopeptides.

• a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Kondensationsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Kondensationsverbindung.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form a chemical bond linking both components. Furthermore, those compounds according to the invention are also included as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to component B is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with

• a) amines and derivatives thereof to form imines or oximes as a condensation compound
• b) of alcohols to form acetals or ketals as a condensation compound.

Component A is preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydoxyacetophenone, 2,4, 6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2- Aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4 , 4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7- Trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone,
Vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxybenzaldehyde 2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy 4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3 Ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6- Dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-T trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2, 4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino 2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy- 1-napthalde hyd, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3, 4-Dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy 4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamic aldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- Dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7- Tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolealdehyde , 3-indole-aldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-Ac etylindole, 1-methyl-3-acetylindole, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde , 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl trifluoroacetone, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde,
1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone, benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4- Methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene ) -2,4-pentanedione, 2-benzylidenecyclohexanone, 2- (4'-hydroxybenzylidene) -cyclohexanone, 2- (4'-dimethylaminobenzylidene) -cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2- (4'- Hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5 , 5-dimethyl-1,3-cyclohexanedione, 2- ( 4'-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2'- (4-hydroxybenzylidene) cyclopentanone, 2- (4'-dimethylaminobenzylidene) cyclopentanone,
5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3, 4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl ) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal,
6- (4-Dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5 -dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6 - (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5- dien-2-one,
5- (4-Dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy 3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3 -nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde , 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1 -naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9 -methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolal hyde,
4-Formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1 benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1 methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8- Formyl 1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium; 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6-formyl-1 allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6-acetyl-1-methyl-quinolinium, 7-acetyl-1-methyl-quinolinium, 8- Acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-Acetyl-1-benzyl-quinolinium, 7-acetyl-1-benzyl-quinolinium, 8-acetyl-1-benzyl-quinolinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl-1 allyl quinolinium and 8-acetyl-1-allyl quinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1,3-dimethyl-2- (4'-formylphenyl) benzimidazolium - 1,3-Dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4 '-Formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5 -Chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazoliumbenzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate,
Isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5- Carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

When CH-Acids are generally considered to be compounds which a hydrogen atom bonded to an aliphatic carbon atom carry, due to electron-withdrawing substituents one Activation of the corresponding carbon-hydrogen bond causes becomes. According to the invention, CH-acidic compounds also include enamines. by alkaline treatment of quaternized N-heterocycles with a conjugated to quaternary nitrogen CH-acid Alkyl group arise.

The CH-acidic compounds of component B are preferably selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-Tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, oxindole, 3-indoxylacetate, 2-coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1,2-dione, Indan-1,3-dione, indan-1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulphonate, 1-ethyl-2-methylquinolinium p-toluenesulphonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate. Especially preferred CH-acidic compounds are 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidiniumchlorid, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4,6-dimethyl-2-oxo -pyrimidiniumhydrogensulfat, 1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3- diethyl-4-methyl-2-oxo-pyrimidiniumchlorid, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidiniumhydrogensulfat, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidiniumchlorid, 1,2-Dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium chloride and 1,2-dihydro-1,3-bis (2-hydroxyethyl) -4-methyl-2-oxopyrimidinium hydrogensulfate.

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

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group 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,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 C 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 hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

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

• – 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.

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

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 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 castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _{x :} These compounds are characterized by the following parameters.

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

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

• – 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.

Particular preference is given to those alkylpolyglycosides in which R ¹

• Consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• Essentially of 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.

When Sugar component Z can any mono- or oligosaccharides are used. Usually Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Such sugars are, for example, glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, Gulose, idose, talose and sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The usable according to the invention Alkyl polyglycosides contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x 1.1 to 1.4.

The Alkyl glycosides can in addition to their surfactant effect also serve the fixation of fragrance components to improve on the hair. The person skilled in the art will therefore be that one over the effect of the perfume oil beyond the duration of the hair treatment the hair desired is, preferably to this class of substance as a further ingredient the preparations according to the invention To fall back on.

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

Furthermore, zwitterionic surfactants can be used, in particular as 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 N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethyl carboxymethylglycinat. 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 understood as meaning 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 are capable of forming internal salts. 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, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention as cationic surfactants, especially those of the quaternary ammonium type, the esterquats and amidoamines used.

preferred quaternary Ammonium compounds are ammonium halides, especially chlorides and Bromides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid 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.

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

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

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

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

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

at it may be the compounds with alkyl groups used as surfactant each are uniform substances. It is, however, in usually preferred in the preparation of these substances by native to go out with vegetable or animal raw materials, so that one Substance mixtures with different, from the respective raw material dependent alkyl chain lengths receives.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may 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-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyltrimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methylmethacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methyl vinylether/Malein-säureanhydrid-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 Hydrokolloid 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,
• – Parfümöle, 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-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, 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, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- 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,

enthaltenFurthermore, the colorants according to the invention further active ingredients, auxiliaries and additives, such as

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers, 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. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloid such as polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, 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,
• - 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 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, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer 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 further optional components as well as the amounts of these components used expressly on the specialist manuals known to those skilled in the art, eg. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

The agents according to the invention contain the compounds according to formula I preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. To the Purposes of hair coloring are such carriers For example, creams, emulsions, gels or surfactant-containing foaming Solutions, such as shampoos, foam aerosols or other preparations, the for the application on the hair are suitable. But it is also conceivable the dye precursors in a powdered or tablet-like formulation to 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.

A oxidative staining The fibers may be in the presence of oxidation dye precursors in principle done with atmospheric oxygen. However, preference is given to a chemical Oxidizing agent used, especially if in addition to the staining a Whitening effect on human hair is desired. This whitening effect can be independent from the staining method required be. The presence of oxidation dye precursors is accordingly no mandatory requirement for an employment of oxidizing agents in the agents according to the invention. The oxidizing agents are persulfates, chlorites and in particular Hydrogen peroxide or its addition products to urea, Melamine and sodium borate in question.

However, according to the invention the oxidation colorant also be applied to the hair together with a catalyst, the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates.

By Use of these metal salts can both accelerate the formation of staining as well as the color shade can be influenced.

• – Pyranose-Oxidase und z.B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention, with the aid of Atmospheric oxygen directly oxidize the oxidation dye precursors, such as the laccases, or generate in situ small amounts of hydrogen peroxide and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

• Pyranose oxidase and eg D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• Alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

at An application of oxidants becomes the actual colorant expediently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the compounds of formula I and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12 have. Particularly preferred the application of hair dye in a slightly alkaline environment. The application temperatures can in a range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes will be the hair dye by rinsing of which to be colored Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, e.g. a dyeing shampoo, has been used.

Especially in hard-to-dye Hair may be an agent of the invention optionally with additional Dye precursors but also without prior mixing with the Oxidation component to be applied to the hair. After a Einwirkdauer of 20 to 30 minutes will then - if necessary after a Intermediate rinse - the oxidation component applied. After another exposure time of 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors to effect a better penetration into the hair, the corresponding Medium adjusted to a pH of about 4 to 7. According to one second variant is first an air oxidation, with the applied agent being preferred a pH of 7 to 10. In the subsequent accelerated post-oxidation may be the use of acidified peroxidisulfate solutions as Oxidizing agent may be preferred.

• – gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann
• – ein Tönungs- oder Färbemittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird,
• – dieses Färbemittel M2 nach einer Zeit von 5-30 Minuten von der Faser abgespült wird
• – und nach der Behandlung gegebenenfalls ein Nachbehandlungsmittel M4 auf die Faser aufgetragen und nach einer Einwirkzeit von einigen Minuten wieder abgespült wird,

wobei mindestens eines der Mittel M1, M2, M3 oder M4 mindestens eine Verbindung gemäß Formel (I) oder eines oder mehrere ihrer Salze mit einer anorganischen oder organischen Säure enthält

in der R1 und R2 unabhängig voneinander für ein Wasserstoffatom, eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine substituierte oder unsubstituierte Arylgruppe, eine substituierte oder unsubstituierte Heteroarylgruppe, eine Arylalkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine Aminoalkylgruppe, eine Dialkylaminoalkylgruppe stehen, wobei die Reste R1 und R2 gemeinsam einen gesättigten Ring bilden können, der weitere Heteroatome wie N oder O enthalten kann und der Rest R3 für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine Hydroxygruppe, eine Aminogruppe, eine Dialkylaminogruppe, eine C₁-C₆-Alkoxygruppe, eine Nitrogruppe, eine Hydroxy-C₁-C₆-alkoxygruppe, eine Carboxygruppe, eine Sulfonylgruppe, eine Sulfonamidogruppe oder eine Carboxamidogruppe stehen und in der n für 3, 4 oder 5 steht.A second object of the present invention is a process for tinting and / or dyeing keratin fibers, in particular human hair, in which

• - If desired, a pretreatment agent M1 is applied to the fiber, then
• A tinting or dyeing agent M2 is applied to the fiber, wherein, if desired, an additional agent M3 is added to the agent M2 before use,
• - This colorant M2 is rinsed from the fiber after a time of 5-30 minutes
• - and after the treatment optionally a post-treatment agent M4 applied to the fiber and rinsed again after a contact time of a few minutes,

wherein at least one of the agents M1, M2, M3 or M4 comprises at least one compound according to formula (I) or one or more of its salts with an inorganic or organic acid

in the R _{1 and} R ₂ independently of one another represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ polyhydro xyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, wherein the radicals R _{1 and} R ₂ may together form a saturated ring which may contain further heteroatoms such as N or O and the R3 is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ alkoxy group, a nitro group, a hydroxy -C ₁ -C ₆ alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in the n stands for 3, 4 or 5.

In preferred according to the invention Method is to Means M2 shortly before use a means M3 containing at least one compound according to formula (I), admitted.

Especially preferred method according to the invention are characterized in that the agent M3 is a preparation according to the invention is.

in der R1 und R2 unabhängig voneinander für ein Wasserstoffatom, eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine substituierte oder unsubstituierte Arylgruppe, eine substituierte oder unsubstituierte Heteroarylgruppe, eine Arylalkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine Aminoalkylgruppe, eine Dialkylaminoalkylgruppe, stehen, wobei die Reste R1 und R2 gemeinsam einen gesättigten Ring bilden können, der weitere Heteroatome wie N oder O enthalten kann und der Rest R3 für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine Hydroxygruppe, eine Aminogruppe, eine Dialkylaminogruppe, eine C₁-C₆-Alkoxygruppe, eine Nitrogruppe, eine Hydroxy-C₁-C₆-alkoxygruppe, eine Carboxygruppe, eine Sulfonylgruppe, eine Sulfonamidogruppe oder eine Carboxamidogruppe stehen und in der n für 3, 4 oder 5 steht, in kosmetischen Mitteln.A third object of the present invention is the use of compounds of formula (I) or one or more of their salts with an inorganic or organic acid

in the R _{1 and} R ₂ independently of one another represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, wherein the radicals R _{1 and} R ₂ together form a saturated ring which may contain further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ alkoxy group, a nitro group, a hydroxy C ₁ -C ₆ alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and wherein n is 3, 4 or 5, in kosm essential agents.

preferred uses according to the invention are characterized in that the A compound of the formula (I) in agents for application to keratin fibers, especially in means for sounding and / or coloring of Keratin fibers, especially human hair, is used.

With regard to more preferred embodiments the method according to the invention and the use according to the invention applies mutatis mutandis to the means according to the invention carried out above.

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

1st Synthesis Example

Synthesis of 4-amino-5,6,7,8-tetrahydro-1-naphthylamine (E1)

In 24.9 g (0.143 mol) of sulphanilic acid in 72 are added to a beaker 2N sodium hydroxide solution and suspended with a solution of 9.8 g (0.143 mol) Sodium nitrite in 120 ml of water. It is stirred until complete dissolution. Then be under ice-salt cooling at 0-5 ° C 125 ml of ten percent hydrochloric acid dropped within one hour. After this is a yellow Suspension of the diazonium salt obtained.

The Suspension of the diazonium salt is brought under ice-salt cooling (0-5 ° C) within from 30 minutes to a solution of 21 g (0.143 mol) of 5,6,7,8-tetrahydro-1-naphthylamine dripped into 800 ml of half-concentrated hydrochloric acid. After a stirring time of 1.5 hours to the reaction solution 75.7 g (0.382 mol) of sodium dithionite added. Then it is heated to 75 ° C for 20 minutes.

After cooling to room temperature, a pH of 11 is set by dropwise addition of concentrated sodium hydroxide solution. If the temperature of the reaction solution exceeds 20 ° C, it is cooled with ice water. The precipitated blue-violet solid is filtered off and washed with plenty of water. After recrystallization from water, a white solid is obtained.
Yield: 18.6 g (80%)
Mp 78 ° C (Ref. [2]: 83 ° C)

2. Application examples

I) Preparation of the coloring cream

Partial mixture A: Hydrenol ^® D 8.50 g Lorol® ^® techn. 2,00 g Eumulgin ^® B2 0.75 g Texapon.RTM ^® NSO 20.00 g Dehyton ^® K 12.50 g water 30.00 g

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

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 (Partial Mixture B) was added to the emulsion (Mixture A) with ammonia adjusted 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 the table below.

Claims (14)

Oxidation colorant for dyeing keratin fibers, in particular human hair, containing at least one coupler component and at least one developer component in a hydrous carrier, characterized in that - the coupler component is selected from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted Pyridine derivatives and - the developer component is selected from the compounds according to formula (I),

in the R _{1 and} R ₂ independently of one another represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, wherein the radicals R _{1 and} R ₂ together form a saturated ring which may contain further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ alkoxy group, a nitro group, a hydroxy-C ₁ -C ₆ alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in which n is 3, 4 or 5, and de salts with an inorganic or organic acid. An oxidation according to claim 1, characterized in that it comprises a developer component of Contains formula (I), in the n for 3 or 4 stands. An oxidation according to one of the claims 1 or 2, characterized in that it is a developer component contains the formula (I), in which the radicals R1, R2 and R3 for represent a hydrogen atom. An oxidation according to one of the claims 1 to 3, characterized in that the compound according to formula (I) selected is from 4-amino-5,6,7,8-tetrahydro-1-naphthylamine and / or 7-amino-2,3-dihydro-1H-inden-4-ylamine. Oxidation colorant according to one of Claims 1 to 4, characterized in that, besides the coupler components, it is selected from the group consisting of m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol vate, pyrazolones, m-aminophenols and substituted pyridine derivatives and the compounds of the formula (I) contains no further oxidation dye precursors. An oxidation according to one of the claims 1 to 5, characterized in that it is a further developer component contains the selected is from 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-diaminophenoxy) ethanol, N, N-bis (2'-hydroxyethyl) -1,4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 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, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole and N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine trihydrochloride. An oxidation according to one of the claims 1 to 4 or 6, characterized in that the coupler component is selected from resorcinol, 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1,3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methyl-resorcinol, 2,5-dimethylresorcinol and 4-chlororesorcinol 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, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-Amino-4- (2-methoxyethoxy) -5-methylphenylamine and 2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol dihydrochloride. An oxidation according to one of the claims 1 to 7, characterized in that it contains the coupler component (s) in an amount of 0.01 to 20% by weight, preferably 0.5 to 5% by weight, and the developer component (s) in an amount of 0.01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, each based on the entire oxidation dye, contains. An oxidation according to one of the claims 1 to 8, characterized in that it has at least one substantive Contains dye, the selected is from nitrophenylenediamines, nitroaminophenols, azo dyes, Anthraquinones or indophenols, preferably from the group of known under international names or trade names Dyes HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-Amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic and their salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. A method for tinting and / or dyeing keratin fibers, in particular human hair, in which - if desired, a pretreatment agent M1 is applied to the fiber, then - a tinting or coloring agent M2 is applied to the fiber, wherein, if desired, the agent M2 before use a further agent M3 is added, - this colorant M2 is rinsed off the fiber after a time of 5-30 minutes - and after the treatment optionally an aftertreatment agent M4 is applied to the fiber and rinsed off after a contact time of a few minutes, characterized in that at least one of the agents M1, M2, M3 or M4 contains at least one compound of the formula (I) or one or more of its salts with an inorganic or organic acid

in the R _{1 and} R ₂ independently of one another represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, wherein the radicals R _{1 and} R ₂ together form a saturated ring which may contain further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ alkoxy group, a nitro group, a hydroxy C ₁ -C ₆ alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and in which n is 3, 4 or 5. Method according to claim 10, characterized in that that the Means M2 shortly before use M3 agent containing at least a compound according to formula (I), is added. Method according to one of claims 10 or 11, characterized that this M3 means a preparation according to a the claims 1 to 9 is. Use of compounds of the formula. (I) or one or more of its salts with an inorganic or organic acid

in the R _{1 and} R ₂ independently of one another represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an arylalkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, an aminoalkyl group, a dialkylaminoalkyl group, wherein the radicals R _{1 and} R ₂ together form a saturated ring which may contain further heteroatoms such as N or O and the radical R3 is a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a hydroxy group, an amino group, a dialkylamino group, a C ₁ -C ₆ alkoxy group, a nitro group, a hydroxy C ₁ -C ₆ alkoxy group, a carboxy group, a sulfonyl group, a sulfonamido group or a carboxamido group and wherein n is 3, 4 or 5, in kosm essential agents. Use according to claim 13, characterized that the A compound of the formula (I) in agents for application to keratin fibers, especially in means for sounding and / or dyeing of keratin fibers, especially human hair becomes.