DE102010030434A1 - Composition, useful for coloring and optionally simultaneous lightening of keratin fibers, preferably human hair, comprises a cationic compound containing a substituted dimethyl-(2-oxo-(1,3)dioxolan-4-yl-methyl)-ammonium compounds - Google Patents

Abstract

Composition comprises at least one cationic compound containing substituted dimethyl-(2-oxo-[1,3]dioxolan-4-yl-methyl)-ammonium compounds (I). Composition comprises at least one cationic compound containing substituted dimethyl-(2-oxo-[1,3]dioxolan-4-yl-methyl)-ammonium compounds of formula (I). CHR : a chromophore comprising anthraquinone-, azo-, naphthoquinone-, triarylmethane-, nitrophenylenediamine-, nitroaminophenol-, phenazine-, oxazine- or thiazine-dyes; L : a linker comprising -(CH 2) n-, -(CH 2) n-O-(CH 2) m-, -(CH 2) n-N(R1)-(CH 2) m-, -(CH 2) n-C(=O)-O-(CH 2) m-, -(CH 2) n-C(=O)-N(R1)-(CH 2) m- or -(CH 2) n-S(=O) 2-N(R1)-(CH 2) m-; n1 : 2-6; R1 : H, 1-6C-alkyl, 2-6C-alkenyl or 2-6C-hydroxyalkyl, where the bond between the chromophore and the linker takes place by carbon-, nitrogen-, oxygen- or sulfur-atom at the available chromophore; and X ->monovalent anion, preferably halide, hydrogen sulfate, 1/2 sulfate, p-benzene sulfonate, p-toluene sulfonate, acetate, tetrafluoroborate, trifluoromethane sulfonate, hexafluorophosphate, methanesulfate or methanesulfonate. Independent claims are included for: (1) coloring and possibly simultaneous lightening of keratin fibers, preferably human hair, comprising if desired, applying a pretreatment agent-M1 on the fiber, applying an agent-M2 on the fiber, where if desired, an another agent-M3 is added with the agent-M2 prior to use, rinsing the agent-M2 after a period of 5-30 minutes from the fiber, and after the treatment, optionally applying an after treatment agent-M4 on the fiber and rinsing after an exposure of some minutes, where at least one of the agent of M1-M4 is the composition; and (2) the compound (I). [Image].

Description

The invention relates to novel cationic dyes and agents for dyeing and optionally simultaneous brightening of keratin-containing fibers, in particular human hair containing these dyes, the use of these cationic dyes for dyeing hair and a method for dyeing keratin fibers, in particular human hair.

For the dyeing of keratin-containing fibers, either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are generally used. Coupler and developer components are also referred to as oxidation dye precursors.

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

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl ) -ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 4,5-diamino 1- (2-hydroxyethyl) pyrazole.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used. Suitable coupler substances are in particular α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis ( 2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

Although intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H ₂ O ₂ , which in some cases may result in damage to the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes sensitize people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage lies in the fact that the dyes often have only insufficient fastness properties.

The object of the present invention is to provide novel substantive dyes which are outstandingly suitable for use in hair dyeing and are distinguished by good fastness properties, such as, for example, light fastness, rubfastness and washfastness as well as perspiration and cold wave fastness. In the case of simultaneous use with oxidation dyes and / or oxidants direct drawers should have sufficient stability against H ₂ O ₂ and not lose their positive fastness and dyeing properties. In addition, the colorants must have no or only a very low sensitizing potential and may under no circumstances be mutagenic. In addition, as bright and intense colors as possible should be achieved.

It has surprisingly been found that compounds of the general formula (I) are very suitable as direct drawers for hair coloring. In colorations, intense yellow, orange, red, purple, blue, brown and natural color shades are obtained with good fastness properties. The Direktzieher also provide with the simultaneous use of oxidizing agents such as hydrogen peroxide or a mixture of hydrogen peroxide and peroxydisulfates bright nuances without attenuation of color intensity and color brilliance. In this way, the simultaneous lightening and coloring of hair is possible, which also on dark hair, a bright color can be achieved.

Colorants containing compounds of the following formula (I) and some of the corresponding compounds themselves are not yet known.

in der
CHR für einen Chromophor steht, der ausgewählt ist aus Anthrachinonfarbstoffen, Azofarbstoffen, Naphthochinonfarbstoffen, Triarylmethanfarbstoffen, Nitrophenylendiaminfarbstoffen, Nitroaminophenolfarbstoffen, Phenazinfarbstoffen, Oxazinfarbstoffen oder Thiazinfarbstoffen
L stellt eine Linker-Gruppierung dar, ausgewählt aus Strukturen der Formeln (II) bis (VII)

wobei n und m hierbei unabhängig voneinander eine ganze Zahl von 2 bis 6 darstellen und der Rest R1 für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe steht, und
wobei die Bindung zwischen Chromophor und Linker über ein am Chromophor vorhandenes Kohlenstoffatom, Stickstoffatom, Sauerstoffatom oder Schwefelatom erfolgt,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, p-Benzolsulfonat, p-Toluolsulfonat, Acetat, Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat. The present invention relates, in a first embodiment, to agents for dyeing and optionally simultaneously brightening keratin fibers, in particular human hair, containing at least one cationic compound of the formula (I):

in the
CHR is a chromophore selected from anthraquinone dyes, azo dyes, naphthoquinone dyes, triarylmethane dyes, nitrophenylenediamine dyes, nitroaminophenol dyes, phenazine dyes, oxazine dyes or thiazine dyes
L represents a linker moiety selected from structures of formulas (II) to (VII)

where n and m independently of one another represent an integer from 2 to 6 and the radical R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group , and
the bond between the chromophore and the linker being via a carbon atom, nitrogen atom, oxygen atom or sulfur atom present on the chromophore,
X ^- represents a monovalent anion, preferably halide, hydrogen sulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate.

It is preferred if a linker of one of the structures (II) or (III), in particular of the structure (II), the chromophore with the cationic dimethyl [(2-oxo-1,3-dioxolan-4-yl) methyl] ammonium Grouping connects.

Keratin fibers are wool, furs, feathers and especially human hair to understand. The colorants of the invention can in principle but also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers such. As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used.

The term "dyeing of keratin fibers" used in the invention includes any form of color change of the fibers. Included are in particular those covered by the terms tinting, bleaching, oxidative staining, semipermanent staining, permanent staining and temporary staining Color changes. Explicitly included in accordance with the invention are color changes which have a lighter color result compared to the starting color, such as bleaching, for example.

Examples of (C ₁ to C ₆ ) -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals.

Examples of corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl.

Examples of preferred (C ₂ to C ₆ ) alkenyl radicals are vinyl and allyl.

Further, as preferable examples of a (C ₁ to C ₆ ) monohydroxyalkyl group, there may be mentioned hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6 Be called hydroxyethyl group. A 2-hydroxyethyl group is particularly preferred.

Examples of a (C ₂ to C ₆ ) polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

Preferred (C ₁ to C ₆ ) alkoxy groups according to the invention are, for example, a methoxy or an ethoxy group.

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and methoxyhexyl groups are examples of (C ₁ to C ₆ ) alkoxy (C ₂ to C ₆ ) alkyl groups according to the invention.

A preferred hydroxy (C ₁ -C ₆ ) alkoxy group is the 2-hydroxyethoxy group.

Examples of halogen atoms are F, Cl, Br or I atoms, with Br or Cl atoms being very particularly preferred.

The aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl, dimethylamino, 1-piperidinomethyl, 1-pyrrolidinomethyl, 4-morpholinomethyl, bis (2-hydroxyethyl) amino and the amino group

Examples of a group R ⁵ R ⁶ N- (CH ₂ ) _n -, wherein the diethylaminomethyl, 1-piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and the amino group are particularly preferred. Preferred aryl (C ₁ to C ₆ ) alkyl groups are benzyl and 2-phenylethyl.

In a first preferred embodiment of the present invention, the compounds of the formula (I) contain as chromophore CHR an anthraquinone dye which preferably corresponds to the following formula (VIII).

in der
R1 für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe steht,
R2, R3 unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkoxygruppe oder eine C₁-C₆-Alkylgruppe stehen.According to preferred means for dyeing and optionally simultaneous brightening of keratinic fibers are therefore characterized in that the compounds of the formula (I) have as chromophore CHR an anthraquinone dye which is preferably selected from structures of the formula (VIII)

in the
R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group,
R 2, R 3 independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkoxy group or a C ₁ -C ₆ -alkyl group.

• – Salze des 3-[(4-Amino-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-3-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-2-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 2-[(4-Amino-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-3-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-2-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  

In the context of this first preferred embodiment, the following compounds are particularly suitable for achieving the object according to the invention: Particularly preferred agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers comprise at least one cationic compound from the group of

• Salts of 3 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane 4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-3-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 2 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-3-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  

Within this group, the physiologically tolerable salts of 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl are to be emphasized as being particularly suitable N - [(2-oxo-1,3-dioxolan-4-yl) methyl] propanaminiums:
3 - [(-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl 4) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane -4-yl) methyl] propanaminium p-toluenesulfonate
3 - [(-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl 4) amino] -N, N-dimethyl- N - [(2-oxo-1,3-dioxolane -4-yl) methyl] propanaminiumbenzolsulfonat
3 - [(-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl 4) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane -4-yl) methyl] propanaminium
3 - [(-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl 4) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane -4-yl) methyl] propanaminium
3 - [(-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl 4) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane -4-yl) methyl] propanaminiumhydrogensulfat

Further particularly preferred salts are listed explicitly below in the disclosure of the compounds per se. Compositions according to the invention containing the salts disclosed therein are also particularly preferred.

in der
A ein carbozyklisches oder heterozyklisches, gegebenenfalls substituiertes, ungeladenes Ringsystem darstellt,
R1 für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe steht,
R2, R3 unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkoxygruppe oder eine C₁-C₆-Alkylgruppe stehen.In a second preferred embodiment, the chromophore CHR is an azo dye. Within the scope of the object of the invention, it is particularly advantageous if this azo dye corresponds to the structure (IX). Compositions preferred according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are characterized in that the compounds of the formula (I) have, as the chromophore CHR, an azo dye which is preferably selected from structures of the formula (IX)

in the
A represents a carbocyclic or heterocyclic, optionally substituted, uncharged ring system,
R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group,
R 2, R 3 independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkoxy group or a C ₁ -C ₆ -alkyl group.

wobei die Reste R4 und R5 unabhängig voneinander für ein Wasserstoffatom, eine Nitrogruppe, eine Nitrilgruppe, ein Halogenatom, eine C₁-C₆-Alkylsulfonylgruppe, eine Carbamoylgruppe, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Alkoxygruppe oder eine Phenylgruppe stehen.The group A represents a carbocyclic or heterocyclic, optionally substituted, uncharged ring system. It is preferred if A is an optionally substituted heterocycle. In the context of this further particularly advantageous embodiment, A stands for one of the following heterocycles (X) to (XXI): Preferred agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are characterized in that the grouping A in formula (IX) represents an optionally substituted heterocycle, which is preferably selected from heterocycles of the formulas (X) to (XXI)

wherein the radicals R4 and R5 independently of one another represent a hydrogen atom, a nitro group, a nitrile group, a halogen atom, a C ₁ -C ₆ -alkylsulfonyl group, a carbamoyl group, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -alkoxy group or a phenyl group.

• – Salze des N,N-Dimethyl-2-{methyl[4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{ethyl[4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{methyl[3-methyl-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{ethyl[3-methyl-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{methyl[3-chlor-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{ethyl[3-chlor-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-methyl-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{3-methyl-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-chlor-4-[(5-nitro-1,3-thiazol-2-y))diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{3-chlor-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-methyl-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{3-methyl-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-chlor-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{3-chlor-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  

In the context of this second preferred embodiment, the following compounds are particularly suitable for achieving the object according to the invention: Particularly preferred agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers comprise at least one cationic compound from the group of

• Salts of N, N-dimethyl-2- {methyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {ethyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {methyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1,3-dioxolane-4 -yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {ethyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1,3-dioxolane-4 -yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {methyl [3-chloro-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {ethyl [3-chloro-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3 dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3 dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(5-nitro-1,3-thiazol-2-y)) diazenyl] phenyl} amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-chloro-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-methyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-methyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) -diazenyl] -phenyl} -amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-chloro-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) -diazenyl] -phenyl} -amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  

in der
die Reste R1, R1' und R1'' unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe stehen.In a third preferred embodiment, the chromophore CHR is a nitrophenylenediamine dye. In this case, it is particularly advantageous if this nitrophenylenediamine dye corresponds to the substructure (XXII). Preferred colorants according to the invention and optionally simultaneous lightening of keratinic fibers are characterized in that the Compounds of the formula (I) as chromophore CHR have a nitrophenylenediamine dye, which is preferably selected from structures of the formula (XXII)

in the
the radicals R _1, R ₁ 'and R ₁ "independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group.

• – Salze des 2-[(4-Amino-2-nitrophenyl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-3-nitrophenyl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(methylamino)-2-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(methylamino)-3-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(dimethylamino)-2-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(dimethylamino)-3-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[(2-hydroxyethyl)amino]-2-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[(2-hydroxyethyl)amino)-3-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[bis(2-hydroxyethyl)amino]-2-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[bis(2-hydroxyethyl)amino]-3-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  

Particularly preferred compositions according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers comprise at least one cationic compound from the group of

• Salts of 2 - [(4-amino-2-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of 2 - [(4-amino-3-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - {[4- (methylamino) -2-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanamine
  
• Salts of N, N-dimethyl-2 - {[4- (methylamino) -3-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - {[4- (dimethylamino) -2-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - {[4- (dimethylamino) -3-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums
  
• Salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino) -3-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums
  
• Salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethyl) amino] -3-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  

The compositions according to the invention for dyeing and, if appropriate, simultaneous lightening of keratin fibers preferably contain the compound (s) of the formula (I) in amounts above 1 ppm and below 10% by weight, in each case based on the total agent. Preferred agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are characterized in that they contain the compound (s) of the formula (I) in amounts of. 0.001 to 5 wt .-%, preferably from 0.0025 to 2.5 wt .-%, particularly preferably from 0.005 to 1.5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the entire remedy, included.

The agents according to the invention serve to change the color of keratinic fibers, in particular human hair. The color change can be carried out solely on the basis of the cationic compound (s) of the formula (I), but the agents according to the invention may additionally contain further color-modifying substances, for example substantive dyes and / or oxidation dyes. Compositions according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers which additionally contain, based on their weight, from 0.001 to 5% by weight of one or more oxidation dye precursors and / or substantive dyes are preferred.

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings but usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.

These further coloring substances are described below:
As developer components are usually primary aromatic amines with another, located in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

wobei

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

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

in which

• G ¹ represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl, 4'-aminophenyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl;
• G ² represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -hydroxyalkoxy radical, a (C ₁ to C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -acetylaminoalkoxy radical, a mesylamino (C ₁ to C ₄ ) alkoxy or (C ₁ to C ₄ ) carbamoylaminoalkoxy;
• G ⁴ represents a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical or a (C ₁ to C ₄ ) -alkoxy (C ₁ to C ₄ ) -alkyl radical or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine , 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine , N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N Bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- ( α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-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-phenyle ndiamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4 -Amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

Very particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) - p-phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 2-methoxymethyl-p-phenylenediamine and the physiologically acceptable salts of these compounds.

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

wobei:

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

mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.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 are a hydroxyl or NH ₂ radical which is optionally substituted by a (C ₁ to C ₄ ) -alkyl radical, by a (C ₁ to C ₄ ) -hydroxyalkyl radical and / or by a bridge Y is substituted 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 to C ₈ ) alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, - (C ₁ to C ₄ ) -aminoalkyl radical or a direct compound for bridging Y,
• G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a (C ₁ to C ₄ ) -alkyl radical,

with the proviso that the compounds of the formula (E2) contain only one bridge Y per molecule.

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

Preferred dinuclear developing agents of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino -propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N , N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4 '-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis ( 2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

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

wobei:

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

Furthermore, it 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 to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl, (C ₁ to C ₄ ) aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, (C ₁ to C ₄ ) hydroxyalkoxy, a (C ₁ to C ₄ ) hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl radical or a (di - [(C ₁ to C ₄ ) alkyl] amino) - (C ₁ to C ₄ ) alkyl radical, and
• G ¹⁴ is a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical or a (C ₁ to C ₄ ) -cyanoalkyl radical,
• G ¹⁵ is hydrogen, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.

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

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

Furthermore, the developer component may be selected from heterocyclic developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically acceptable salts.

worin

• – G¹⁷, G¹⁸ und G¹⁹ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxygruppe oder eine Aminogruppe steht und
• – G²⁰ für eine Hydroxygruppe oder eine Gruppe -NG²¹G²² steht, worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe,

mit der Maßgabe, dass maximal zwei der Gruppen aus G¹⁷, G¹⁸, C¹⁹ und G²⁰ eine Hydroxygruppe bedeuten und höchstens zwei der Reste G¹⁷, G¹⁸ und G¹⁹ für ein Wasserstoffatom stehen. Dabei ist es wiederum bevorzugt, wenn gemäß Formel (E4) mindestens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Gruppe -NG²¹G²² stehen und höchstens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Hydroxygruppe stehen.Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,

wherein

• G ¹⁷ , G ¹⁸ and G ¹⁹ independently of one another represent a hydrogen atom, a hydroxy group, a (C ₁ to C ₄ ) alkoxy group or an amino group and
• G ^{20 is} a hydroxy group or a group -NG ²¹ G ²² in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group .

with the proviso that a maximum of two of the groups of G ¹⁷ , G ¹⁸ , C ¹⁹ and G ^{20 is} a hydroxy group and at most two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 are} a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a group -NG ²¹ G ²² and at most two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group.

Particularly 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.

worin

• – G²³, G²⁴, G²⁵ stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-(C₁ bis C₄)-alkylgruppe, mit der Maßgabe dass, wenn G²⁵ für ein Wasserstoffatom steht, G²⁶ neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• – G²⁶ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe oder eine (C₂ bis C₄)-Polyhydroxyalkylgruppe und
• – G²⁷ steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.

Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),

wherein

• G ²³ , G ²⁴ , G ²⁵ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -monohydroxyalkyl group, a (C ₂ to C ₄ ) -polyhydroxyalkyl group, a optionally substituted aryl group or an optionally substituted aryl- (C ₁ to C ₄ ) -alkyl group, with the proviso that when G ^{25 is} a hydrogen atom, G ^{26 may} additionally be a group -NH _{2 in} addition to the abovementioned groups,
• G ²⁶ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group or a (C ₂ to C ₄ ) polyhydroxyalkyl group and
• G ²⁷ represents a hydrogen atom, an optionally substituted aryl group, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

Preferably in formula (E5) the radical -NG ²⁵ G ²⁶ binds to the 5 position and the radical G ²⁷ to the 3 position of the pyrazole cycle.

Particularly preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4.5 Diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4.5- Diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable salts.

wobei:

• – G²⁸, G²⁹ und G³⁰, G³¹ unabhängig voneinander stehen für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)-alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Monohydroxyalkyl- oder einen Di[(C₁ bis C₄)-Hydroxyalkyl]-(C₁ bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Hydroxyalkyl- oder einen Di-[(C₁ bis C₄)-hydroxyalkyl]amino-(C₁ bis C₄)-alkylrest, einen Aminorest, einen (C₁ bis C₄)-Alkyl- oder Di-[(C₁ bis 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 NG²⁸G²⁹ und NG³⁰G³¹ 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 NG²⁸G²⁹ (oder NG³⁰G³¹) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and its tautomeric forms, if a tautomeric equilibrium exists:

in which:

• G ²⁸ , G ²⁹ and G ³⁰ , G ³¹ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, an aryl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical is a (C ₁ to C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical which is optionally substituted by an acetyl-ureide or a sulfonyl radical Rest may be protected, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a (C ₁ to C ₄ ) monohydroxyalkyl or a di [(C ₁ to C ₄ ) hydroxyalkyl] - (C ₁ to C ₄ ) aminoalkyl radical,
• The X radicals independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, an aryl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) aminoalkyl radical, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a (C ₁ to C ₄ ) -hydroxyalkyl or a di - [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) alkyl, an amino, a (C ₁ to C ₄ ) alkyl or di - [(C ₁ to C ₄ ) hydroxyalkyl] amino, a halogen atom, a carboxylic acid group or a sulfonic acid group .
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1,

with the proviso that

• The sum of p + q is not equal to 0,
• If p + q equals 2, n has the value 0, and the groups NG ²⁸ G ²⁹ and NG ³⁰ G ³¹ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• If p + q is 1, n is 1, and the groups NG ²⁸ G ²⁹ (or NG ³⁰ G ³¹ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (E7) are defined according to the invention analogously to the above statements.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E6) 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:

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist. In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E7):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;

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

The pyrazolo [1,5-a] pyrimidines of the above formula (E6) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.

Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, N , N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) -methane , 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10-bis- (2,5 -diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, as well as the physiologically acceptable salts of these compounds.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6): Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ ,
-CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C ( CH ₃ ) ₃ .

Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CHCH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) trialkylammonium groups are -N ⁺ (CH ₃ ) ₃ , -N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ), -N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ ,

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ), -CH ₂ CH ₂ CH ₂ -O- CH (CH ₃ ).

Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CHCH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄₎ -Acetylaminoalkoxyreste are -O-CH ₂ NHC (O) CH _3, -O-CH ₂ CH ₂ NHC (O) CH _3, -O-CH ₂ CH ₂ CH ₂ NHC (O ) CH ₃ , -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ .

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄₎ -Cyanoalkylreste are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN.

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH.

Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N ( CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ .

An example of aryl groups is the phenyl group.

Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one coupler component is additionally used when using at least one developer component.

Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. These groups are conjugated by a double bond system. When the cyclic compound is a six-membered ring, said groups are preferably in ortho position or meta position to each other.

• – m-Aminophenol und/oder dessen Derivate,
• – m-Diaminobenzol und/oder dessen Derivate,
• – o-Diaminobenzol und/oder dessen Derivate,
• – Naphthalinderivate mit mindestens einer Hydroxygruppe,
• – Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• – Pyridinderivate,
• – Pyrimidinderivate,
• – Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• – Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• – Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,

Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:

• M-aminophenol and / or its derivatives,
• M-diaminobenzene and / or its derivatives,
• O-diaminobenzene and / or its derivatives,
• Naphthalene derivatives having at least one hydroxy group,
• Di- or trihydroxybenzene and / or derivatives thereof,
• - pyridine derivatives,
• - pyrimidine derivatives,
• Monohydroxyindole derivatives and / or monoamine indole derivatives,
• Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,
• Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Mixtures of two or more compounds from one or more of these classes are also within the scope of this embodiment according to the invention.

worin
G¹ und G² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe,
G³ und G⁴ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),

wherein
G ¹ and G ² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group,
G ³ and G ⁴ independently represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Particularly preferred m-aminophenol coupler components are selected from at least one compound selected from the group consisting of m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6 -methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) - benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all the abovementioned compounds.

worin
G⁵, G⁶, G⁷ und G⁸ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G⁹ und G¹⁰ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe, eine ω-(2,4-Diaminophenyl)-(C₁ bis C₄)-alkylgruppe, eine ω-(2,4-Diaminophenyl)-(C₁ bis C₄)-alkoxygruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),

wherein
G ⁵ , G ⁶ , G ⁷ and G ⁸ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ⁹ and G ¹⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyl) - (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyl) - (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) Polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from 2- (2,4-diaminophenoxy) ethanol, 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, 2 - (3 [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethylamino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({ 3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5- methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of all the compounds mentioned above.

worin
G¹¹, G¹², G¹³ und G¹⁴ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G¹⁵ und G¹⁶ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine Carboxylgruppe, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),

wherein
G ¹¹ , G ¹² , G ¹³ and G ¹⁴ independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ¹⁵ and G ¹⁶ independently of one another represent a hydrogen atom, a halogen atom, a carboxyl group, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) Monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.

worin
G¹⁷ und G¹⁸ stehen unabhängig voneinander für eine Hydroxygruppe oder eine Gruppe -NG²¹G²², worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe,
G¹⁹ und G²⁰ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Alkoxygruppe.The pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),

wherein
G ¹⁷ and G ¹⁸ independently of one another represent a hydroxy group or a group -NG ²¹ G ²² , in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, an optionally substituted aryl group, a (C ₁ to C ₄ ) Alkoxy (C ₁ to C ₄ ) alkyl group,
G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -alkoxy group.

It is preferred if, according to formula (K4), the radicals G ¹⁷ and G ^{18 are} in the ortho position or in the meta position relative to one another.

Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 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, 3,5-diamino-2, 6-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3 -aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.

Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1.3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

worin
G²³ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G²⁴ steht für eine Hydroxygruppe oder eine Gruppe -NG²⁶G²⁷, worin G²⁶ und G²⁷ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G²⁵ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C₄)-Alkylgruppe,
mit der Maßgabe, dass G²⁴ in meta-Position oder ortho-Position zum Strukturfragment NG²³ der Formel bindet.The indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),

wherein
G ²³ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₃ to C ₆ cycloalkyl group, a C ₂ to C ₄ alkenyl group, a C ₁ to C ₄ monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ²⁴ represents a hydroxy group or a group -NG ²⁶ G ²⁷ , in which G ²⁶ and G ²⁷ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{25 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl group,
with the proviso that G ²⁴ binds in the meta position or ortho position to the structural fragment NG ^{23 of} the formula.

Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned compounds.

worin
G²⁸ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G²⁹ steht für eine Hydroxygruppe oder eine Gruppe -NG³¹G³², worin G³¹ und G³² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe,
G³⁰ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C₄)-Alkylgruppe,
mit der Maßgabe, dass G²⁹ in meta-Position oder ortho-Position zum Strukturfragment NG²⁸ der Formel bindet.The indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),

wherein
G ²⁸ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ²⁹ represents a hydroxy group or a group -NG ³¹ G ³² , in which G ³¹ and G ³² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{30 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl group,
with the proviso that G ²⁹ binds in the meta position or ortho position to the structural fragment NG ^{28 of} the formula.

Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.

Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 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 and the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2.6 Dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl ) -amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol, 2,4- Dichloro-3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 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, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5- methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethylamino) -4,5- dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2- methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, Pyrogallol, 1,2,4-trihydroxybenzene, 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, 3,5-diamino-2,6-dimethoxypyridine, 2, 6-Dihydroxy-3,4-dimethylpyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenylamino-3-aminopyridine, 1-naphthol, 2 -Methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1.8 Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyi ndoline, 7-hydroxyindoline, 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 mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorant.

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

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6): Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ ,
-CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C ( CH ₃ ) ₃ .

Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) trialkylammonium groups are -N ⁺ (CH ₃ ) ₃ , -N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ), -N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ ,

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ -O -CH (CH ₃ ) ₂ .

Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CH ₂ CH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄₎ -Acetylaminoalkoxyreste are -O-CH ₂ NHC (O) CH _3, -O-CH ₂ CH ₂ NHC (O) CH _3, -O-CH ₂ CH ₂ CH ₂ NHC (O ) CH ₃ , -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ .

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄₎ -Cyanoalkylreste are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN.

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH.

Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N ( CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ .

An example of aryl groups is the phenyl group.

Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

For temporary dyeings usually dyeing or tinting agents are used, which contain as coloring component so-called direct drawers. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more rapid undesirable change in shade or even a visible, homogeneous color loss occurs much faster.

Furthermore, the agents according to the invention may contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.

Anionic substantive dyes:

Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1 naphthol-7-sulfonic acid disodium salt (CI 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1,3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of mono- and di-sodium Disulfonic acid) (CI 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (CI 13,015, Acid Yellow 9 ), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenynazo) pyrazole-3-carboxylic acid trisodium salt (CI 19.140, Food Yellow No. 4, Acid Yellow 23), 3 - [(4- Phenylamino) phenyl] azobenzenesulfonic acid sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (CI 45.350, Acid Yellow 73, D & C Yellow No. 8), 5 - [(2,4-dinitrophenynamino] -2-phenylaminobenzenesulfonic acid, sodium salt (CI 10,385; Acid Orange 3), 4 - [(2 , 4-Dihydroxyphenyl) azo] -benzenesulfonic acid sodium salt (C. I. 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15.510, Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [(2,4-) dimethylphenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (CI 20,170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (CI 14,710, Acid Red 4) , 4-hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (CI 14,720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphthalene) 1-yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255, Ponceau 4R, Acid Red 18), 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7 -naphthalene-disulfonic acid trisodium salt (CI 16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (CI 17, 400; Acid Red 33, Red 33), 5- (acetylamino) -4-hydroxy-3 - [(2-methylphenynazo) -2,7-naphthalenedisulfonic acid disodium salt (CI 18.065; Acid Red 35), 2- (3-hydroxy-2,4,5, 7-tetraiodo-dibenzopyran-6-on-9-yl) -benzoic acid disodium salt (CI 4 5,430; Acid Red 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (C.I. I. 45,100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulfonic acid disodium salt (CI 27.290; Acid Red 73), 2 ', 4', 5 ', 7' Tetrabromo-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' - [9H] xanthene] -3-one disodium salt (CI 45.380; Acid Red 87), 2 ', 4', 5 ', 7'-Tetrabromo-4,5,6,7-tetrachloro-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' [9H] xanthene] -3-one disodium salt (CI 45, 410; Acid Red 92), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthen] -3-one disodium salt (CI 45425; Acid Red 95), 2-Hydroxy-3 - ((2-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (CI 15,685, Acid Red 184), 3-hydroxy-4- (3-methyl-5-oxo-1 phenyl-4,5-dihydro-1H-pyrazol-4-ylazo) -naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4-methyl-2-sulfonphenyl) azo] -2-naphthalenecarboxylic acid calcium salt (CI 15.850: 1; Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt ( CI 14,700; Food Red No. 1; Ponceau SX; FD & C Red No. 4), 1,4-bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (CI 61.570, Acid Green 25), bis [4- (dimethylamino) phenyl] - (3, 7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, sodium salt (CI 44,090, Food Green No. 4, Acid Green 50), bis [4- (diethylamino) -phenyl] (2,4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI 42.045, Food Blue No. 3, Acid Blue 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4-disulfophenyl) -carbenium inner Salt, calcium salt (2: 1) (CI 42.051, Acid Blue 3), N- [4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene] -2,5-cyclohexadiene 1-ylidene] -N-ethylbenzene methanaminium hydroxide, inner salt, sodium salt (CI 42.080, Acid Blue 7), (2-sulfophenyl) di [4- (ethyl ((4-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt betaine (CI 42.090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid (CI 62.055, Acid Blue 25), 1-amino- 4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid natr ium salt (C. I. 62045; Acid Blue 62), 2- (1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1H-indole-5-sulfonic acid disodium salt (CI 73.015, Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) amino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium inner salt, sodium salt (CI Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI 60,730, D & C Violet No. 2, Acid Violet 43), Bis [3 nitro-4 - [(4-phenylamino) -3-sulfophenylamino) -phenyl] -sulfone (CI 10.410; Acid Brown 13), 5-amino-4-hydroxy-6 - [(4-nitrophenyl) -azo] -3 (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (CI 20,470, Acid Black 1), 3-hydroxy-4 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1-naphthalene sulfonic acid-chromium complex (3: 2) (CI 15,711, Acid Black 52), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl azo] -1,7-naphthalenedisulfonic acid tetrasodium salt (CI 28,440, Food Black No. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (bromophenol blue).

Preferred anionic substantive dyes are those under the international designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Cationic direct dyes:

Particularly suitable cationic direct dyes are 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (CI 51.175; Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl]. carbenium chloride (CI 42,595, Basic Blue 7), di (4- (dimethylamino) phenyl) (4- (methylphenylamino) naphthalen-1-yl) carbenium chloride (CI 42,563, Basic Blue 8), 3 , 7-Di (dimethylamino) phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI 44.045, Basic Blue 26). , 2 - [(4- (Ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (CI 11.154, Basic Blue 41), 8-amino-2-bromo-5 -hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (CI 56.059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (CI 42,535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (CI 42,520, Basic Violet 2), tri [4- (dimethylamino) -] p henyl] carbenium chloride (C. I. 42,555; Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (CI 45,170, Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI 42.510 Basic Violet 14), 1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 21.010, Basic Brown 4), 1 - [(4-aminophenyl) azo] -7 - (trimethylammonio) -2-naphthol chloride (CI 12.250; Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [(4- Amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (CI 12.251, Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzolaminium chloride (CI 12,605, Basic Orange 69), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI 50.240, Basic Red 2), 1,4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (CI 11.055, Basic Red 22), 2-hydroxy-1 - [(2-methoxyphenylazo) -7- (trimethylammonio) -naphthalene chloride (CI 12,245; Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride chloride (C. I. 41,000; Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (CI 48,055, Basic Yellow 11), 3 -Methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (CI 12,719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium bisulfate ( 1: 1) (CI 42.040, Basic Green 1), di (4- (dimethylamino) phenyl) -phenylmethanol (CI 42,000, Basic Green 4), 1- (2-morpholiniumpropylamino) -4-hydroxy-9,10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom.

• (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 Heterocyclus 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.

Preferred cationic substantive dyes are included

• (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) direct dyes containing a heterocycle having at least one quaternary nitrogen atom, as described for example in the EP-A2-998 908 to which reference is made at this point, are called in the 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 known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

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

Nonionic substantive dyes:

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes.

Suitable blue nitro dyes are in particular:
1,4-Bis [(2-hydroxyethylamino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1- Methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl- (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue 10), 4 - [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl (2-hydroxyethyl) amino] -1 - [(2 -hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3-methyl 4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2), 1- (2-aminoethylamino) -4- [di (2-hydroxyethylamino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.

Suitable red nitro dyes are in particular:
1-Amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and its salts, 1,4-diamino-2-nitrobenzene ( CI 76,070), 4-amino-2-nitrodiphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13), 1-amino-4- [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2-hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino-4- (methylamino) -2- nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) amino] - 3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange 2), 4 - (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange 3), 1-amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] - 2-nitrobenzene (HC Red 10), 5-chloro-1,4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzene zol (HC Red 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 2 Chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2,5-diamino-6 -nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6- (ethylamino) 2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino) -2-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) -3 - [( 2-hydroxyethyl) amino] -2-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red 14 ).

Suitable yellow nitro dyes are in particular:
1,2-diamino-4-nitrobenzene (CI 76,020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4 - [(2,3-dihydroxypropyl) amino] - 3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-Amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy ) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-chloro-2,4-bis [(2-hydroxyethyl) amino ] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-ureidoethyl) amino] -4-nitrobenzene, 1-amino -4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4 - [(2-hydroxyethyl ) amino] -3-nitrobenzene (HC Yellow 12), 4 - [(2 -Hydroxyethyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino] -3-nitrobenzonitrile (HC Yellow 14), 4 - [(2- Hydroxyethyl) amino] -3-nitrobenzamide (HC Yellow 15) 3 - [(2-hydroxyethyl) amino] -4-methyl-1-nitrobenzene, 4-chloro-3 - [(2-hydroxyethyl) amino] -1 nitrobenzene.

Suitable quinone dyes are in particular:
1,4-di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 61.545, Disperse Blue 23), 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (CI 61,505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange 5) , 1-amino-4-hydroxy-9,10-anthraquinone (CI 60.710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 7- Beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (CI 75,470, Natural Red 4), 1 - [(3 Aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), 1,4-diamino-2 -methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 62,500, Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61.100, Disperse Violet 1), 1-amino-4- (methylamino) -9,10-anthraquinone (CI 61,105, Disperse Viole t 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N- {6 - [( 3-chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500, Natural Brown 7), 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) 3H-indol-3-one (CI 73,000), 4 - {{5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro-5 - [(2-hydroxyethyl) -imino] -1-methyl-1H-pyrazole sulfate (1: 1), hydrate (1: 1).

Suitable neutral azo dyes are in particular:
1- [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (CI 11.210, Disperse Red 17), 1- [di (2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow 7), 2 , 6-diamino-3 - [(pyridin-3-yl) azo] pyridine, 2 - {[4- (acetylamino) phenyl] azo} -4-methylphenol (CI 11855, Disperse Yellow 3), 4 - [(4 Nitrophenyl) azo] -aniline (CI 11.005, Disperse Orange 3).

Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds, and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3 Nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethylamino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic 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-4-nitrophenol.

It is not necessary that the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing or for other reasons, eg. As toxicological, must be excluded.

Furthermore, as direct dyes also naturally occurring dyes may be used, as for example in henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the substrate, e.g. As hair applied; These then form naturally-analogous dyes in the course of oxidative processes in the hair. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The dyeing can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. On the other hand, satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors.

The dyestuff precursors of naturally-analogous dyes are preferably indoles and indolines which have at least two groups selected from hydroxy and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – 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 (RN1),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe 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 (RN2),

in the independently of each other

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

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.

Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

Another possibility for color change is the use of colorants containing so-called Oxofarbstoffvorprodukte. A first class of oxo dye precursors are compounds having at least one reactive carbonyl group. This first class is called a component (Oxo1). A second class of oxo dye precursors form CH-acidic compounds and compounds having primary or secondary amino groups or hydroxy groups, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. This second class is called a component (Oxo2). The aforementioned components (oxo1) and (oxo2) are generally not themselves dyes, and therefore are not in themselves suitable for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process of so-called oxo dyeing. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing.

The Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent in compounds of the component (oxo2). Thus, the oxo staining method can be readily combined with the oxidative staining system.

• – mindestens einer Verbindung, die mindestens eine reaktive Carbonylgruppe enthält (Komponente (Oxo1))

mit mindestens einer Verbindung (Komponente Oxo2)

• – Verbindungen, ausgewählt aus

(Oxo2a) CH-aciden Verbindungen
und/oder aus
(Oxo2b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen
zum Einsatz.As Oxofarbstoffvorprodukte preferably a combination of

• At least one compound containing at least one reactive carbonyl group (component (Oxo1))

with at least one compound (component Oxo2)

• - Connections selected from

(Oxo2a) CH-acidic compounds
and / or out
(Oxo 2b) Compounds having primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds
for use.

• a) von Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente (Oxo1) leitet sich in diesem Fall c) von einem Aldehyd ab)

an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.Reactive carbonyl compounds as component (oxo1) have in the context of the invention at least one carbonyl group as a reactive group which reacts with the component (oxo2) to form a covalent bond. Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group. Furthermore, those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) is always present. These derivatives are preferably addition compounds

• a) amines and derivatives thereof to form imines or oximes as addition compound
• b) of alcohols to form acetals or ketals as addition compound
• c) of water with formation of hydrates as addition compound (component (oxo1) is derived in this case c) from an aldehyde)

to the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred reactive carbonyl compounds of the component (oxo1) are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 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-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2 aldehyde, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, pyridoxal, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl trifluoro-acetone, chromone-3-aldehyde, 3- (5'-nitro-2 '-furyl) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 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, 5- (4-Dimethylamino-1-naphthyl) penta-3,5-dienal, 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-carbazolaldehyde, 6-nitropiperonal, 2-nitropiperonal , 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid,
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, 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-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium-benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 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 Methylquinisatin, as well as any mixtures of the above compounds.

worin

• • R¹, R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine Formylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine (C₁ bis C₆)-Dialkylaminogruppe, eine Di(C₂-C₆-hydroxyalkyl)aminogruppe, eine Di(C₁ bis C₆)-alkoxy-(C₁ bis C₆)-alkyl)aminoguppe, eine (C₁ bis C₆)-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine (C₂ bis C₆)-Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R⁴ und R⁵ stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

Benzaldehyde and / or cinnamaldehyde and / or naphthaldehyde and / or at least one derivative of these abovementioned aldehydes, which in particular carry one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl component in the oxo dyeing. In this case, preference is again given to the reactive carbonyl compound of the component (oxo1) selected from at least one compound of the formula (AC-1),

wherein

• R ¹ , R ² and R ³ are each independently hydrogen, halogen, (C ₁ to C ₆ ) alkyl, (C ₂ to C ₆ ) alkenyl, formyl, hydroxy, C ₁ C ₆ alkoxy group, a (C ₁ to C ₆ ) dialkylamino group, a di (C ₂ -C ₆ hydroxyalkyl) amino group, a di (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl) amino group, (C ₁ to C ₆ ) hydroxyalkyloxy group, sulfonyl group, carboxyl group, sulfonic acid group, sulfonamide group, carbamoyl group, (C ₂ to C ₆ ) acyl group, acetyl group or nitro group,
• Z 'is a direct bond or a vinylene group,
• R ⁴ and R ⁵ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (Oxo1) are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy 1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3 Bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino 2-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dim ethylbenzaldehyde, 4-hydroxy-2,6-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-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, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy- 3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydrox benzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 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-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3, 5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3 Chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4- Dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hyd roxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxy-benzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy 5-ethoxy-4-hydroxybenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4 hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4 hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal.

As CH-acidic compounds are generally considered those compounds which carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond is effected. In principle, there are no limits to the choice of CH-acidic compounds as long as a compound which is visibly colored visibly to the human eye is obtained after condensation with the reactive carbonyl compounds of the component (oxo1). According to the invention, these are preferably those CH-acidic compounds which contain an aromatic and / or a heterocyclic radical. The heterocyclic radical may again be aliphatic or aromatic. The CH-acidic compounds are particularly preferably selected from heterocyclic compounds, in particular cationic, heterocyclic compounds.

worin

• • R⁶ steht für eine lineare oder cyclische (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R⁷ steht für eine (C₁ bis C₆)-Alkylgruppe, insbesondere für eine Methylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion,
• • der Zyklus der Formel (CH-1) repräsentiert alle Ringstrukturen, die zusätzlich weitere Heteroatome wie Stickstoff, Sauerstoff oder Schwefel enthalten können und ferner ankondensierte Ringstrukturen tragen können, wobei alle diese Ringsstrukturen zusätzliche Substituenten tragen können,
• • Het steht für einen gegebenenfalls substituierten Heteroaromaten,
• • X¹ steht für eine direkte Bindung oder eine Carbonylgruppe.

Very particular preference is given to using as component (oxo2a) at least one CH-acidic compound having an aromatic or aliphatic, heterocyclic basic body which is selected from cyclic onium compounds having the structural unit of the formula (CH-1) and / or compounds of the formula (CH-) 2)

wherein

• R ⁶ is a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group, a group R ^I R ^{II is} N- (CH ₂ ) _m -, in which R ^I and R ^II independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -hydroxyalkyl group or an aryl- ( C ₁ to C ₆ ) -alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ⁷ is a (C ₁ to C ₆ ) -alkyl group, in particular a methyl group,
• • X ^- is a physiologically acceptable anion,
• The cycle of the formula (CH-1) represents all ring structures which may additionally contain other heteroatoms such as nitrogen, oxygen or sulfur and may further carry fused ring structures, all of these ring structures being able to carry additional substituents,
• Het is an optionally substituted heteroaromatic,
• • X ¹ represents a direct bond or a carbonyl group.

Preferred ring structures which carry the structural unit of the formula (CH-1) are preferably selected according to the invention from 3H-indolium, benzothiazolium, benzoxazolium, 1,2-dihydro-2-oxopyrimidinium, quinolinium, quinoxalinium or pyridinium.

According to the invention, compounds of the formula (CH-2) are particularly suitable for those in which the radical Het according to formula (CH-2) is derived from one of the heteroaromatic compounds furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine , Pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline , Isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine or coumarin, the aforementioned heteroaromatics having at least one group selected from a halogen atom, a nitro group, a thio group, a thio (C ₁ to C ₆ ) alkyl group, a heteroaryl group, an aryl group, a (C ₁ to C ₆ ) alkyl group, a (C ₁ b is C ₆ ) -alkoxy, hydroxy, (C ₂ to C ₆ ) -hydroxyalkyl, (C ₂ to C ₆ ) -polyhydroxyalkyl, (C ₁ to C ₆ ) -alkoxy (C ₁ to C ₆ ) alkyl group, an aryl (C ₁ to C ₆ ) alkyl group, an amino group, a (C ₁ to C ₆ ) monoalkylamino group, a (C ₁ to C ₆ ) dialkylamino group, a dialkylaminoalkyl group - (CH ₂ ) _n - NR'R '', where n is an integer of 2 and 6 and R ' and R "independently represent a linear or branched alkyl group, which may optionally together form a ring, may be substituted.

Preferably, the compounds of formula (CH-2) are selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl -2-trifluoromethyl-3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-Fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2 -thenoyl) acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H- Benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indole- 3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcoumarin, 2- (2-isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl-5,6- benzoquinolin-4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumarone-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro -1 -benzofuran-2-carboxylic acid tert -butyl ester, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl-1,4-dihydrothiochromeno [4 , 3-c] pyrazol-3-oyl) -acetonitrile.

worin

• • R⁸ und R⁹ stehen unabhängig voneinander für eine lineare oder cyclische (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R¹⁰ und R¹² stehen unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe, wobei mindestens einer der Reste R¹⁰ und R¹² eine (C₁ bis C₆)-Alkylgruppe bedeutet,
• • R¹¹ steht für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxygruppe, eine (C₁ bis C₆)-Hydroxyalkoxygruppe, eine Gruppe R^IIIR^IVN-(CH₂)_q-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe und q steht für eine Zahl 1, 2, 3, 4, 5 oder 6, wobei der Rest R¹¹ zusammen mit einem der Reste R¹⁰ oder R¹² einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer (C₁ bis C₆)-Alkylgruppe, einer (C₁ bis C₆)-Hydroxyalkylgruppe, einer (C₂ bis C₆)-Polyhydroxyalkylgruppe, einer (C₁ bis C₆)-Alkoxygruppe, einer (C₁ bis C₆)-Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe R^VR^VIN-(CH₂)_s-, worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe und s steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6 substituiert sein kann,
• • Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR^VII worin R^VII steht für ein Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine (C₁ bis C₆)-Alkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion.

The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are preferably selected from at least one compound of the formula (CH-3),

wherein

• R ⁸ and R ⁹ are each independently a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group , a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) hydroxyalkyl group or an aryl (C ₁ to C ₄ ) alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ¹⁰ and R ¹² independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, where at least one of the radicals R ¹⁰ and R ¹² denotes a (C ₁ to C ₆ ) -alkyl group,
• R ¹¹ represents a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a (C ₂ to C ₆ ) -polyhydroxyalkyl group, a (C ₁ to C ₆ ) - Alkoxy group, a (C ₁ to C ₆ ) -hydroxyalkoxy group, a group R ^III R ^IV N- (CH ₂ ) _q -, in which R ^III and R ^IV independently of one another represent a hydrogen atom, a (C ₁ to C ₆ ) - Alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group or an aryl (C ₁ to C ₆ ) alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of the radicals R ¹⁰ or R ^{12 may form} a 5- or 6-membered aromatic ring optionally substituted by a halogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a ( C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy group, a (C ₁ to C ₆ ) hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _s - wherein R ^V and R ^VI are independently is a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group or an aryl (C ₁ to C ₆ ) -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
• Y is an oxygen atom, a sulfur atom or a group NR ^VII in which R ^VII represents a hydrogen atom, an aryl group, a heteroaryl group, a (C ₁ to C ₆ ) alkyl group or an aryl (C ₁ to C ₆ ) alkyl group,
• • X ^- stands for a physiologically compatible anion.

At least one group R ¹⁰ or R ¹² according to formula (CH-3) necessarily stands for a (C ₁ to C ₆ ) -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its α-carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R ¹⁰ and R ¹² are each independently hydrogen or a methyl group, wherein at least one group R ¹⁰ or R ^{12 is} a methyl group.

In a preferred embodiment, Y of the formula (CH-3) is an oxygen or a sulfur atom, more preferably an oxygen atom.

The radical R ^{8 of} the formula (CH-3) is preferably selected from a (C ₁ to C ₆ ) -alkyl group (particularly preferably a methyl group), a (C ₂ to C ₆ ) -alkenyl group (in particular an allyl group), a ( C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

R ^{11 of} the formula (CH-3) is preferably a hydrogen atom.

Particularly preferred in formula (CH-3) are the radicals R ⁹ , R ¹⁰ and R ^{12 is} a methyl group, the radical R ^{11 is} a hydrogen atom, Y is an oxygen or sulfur atom and the radical R ⁸ is selected from a ( C ₁ to C ₆ ) alkyl group (particularly preferably a methyl group), a (C ₂ to C ₆ ) alkenyl group (especially an allyl group), a (C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or a optionally substituted benzyl group.

Preferably, the compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidiniums,
1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and
1,2-dihydro-3,4-dimethyl-2-thioxo-chinazoliniums.

Very particularly preferred compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium and
1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums.

X ^- is in the formulas (CH-1) and (CH-3) and in the above lists preferably for halide, benzenesulfonate, p-toluenesulfonate, (C ₁ to C ₄ ) alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate, Tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X ^- .

Compounds of the formula (CH-3) are particularly preferably used according to the invention.

The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are most preferably selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-Methyl-2-trifluoromethyl-3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3 -Thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazole 2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- ( 2-methyl-indol-3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcoumarin, 2- (2-isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2- Phenyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumaron-2-yl) -ac etonitrile, tert-butyl 6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro-1-benzofuran-2-carboxylate, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran 5-oyl) -acetonitrile, 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) -acetonitrile, 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, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p Toluenesulfonate, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methylquinolinium iodide, 1 Ethyl 2-methylquinolinium iodide, 1,2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl quinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, 1,2,3-trimethylquinoxaluminum p-toluenesulfonate, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2 oxopyrimidinium chloride, 1,2-dihydr o-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium chloride, 1, 2-Dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium hydrogen sulfate, 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 hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium chloride, 1,2-Dihydro-1,3,4-trimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium chloride, 1,2- Dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydrochloride 1,3-dipropyl-4-methyl-2-oxopyrimidinium hydrogen sulfate, 1,2 Dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1.2 Dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1.2 Dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro -1,3,4-trimethyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3 diethyl-4-methyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium chloride and 1,2-dihydro-1,3-dipropyl -4-methyl-2-thioxo-pyrimidinium hydrogen sulfate.

Furthermore, as component (Oxo2b) at least one oxidation dye precursor having at least one primary or secondary amino group and / or at least one hydroxyl group can be used. Preferred suitable representatives are found under the execution of the oxidation dye precursors. However, it is preferred according to the invention if the compounds of the component (oxo2) are selected only among CH-acidic compounds.

The above-mentioned compounds of component (Oxo1) and the component (Oxo2) are, when used, each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total Means, used.

The agents according to the invention additionally preferably comprise hydrogen peroxide. Here, agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are particularly preferred, which contain 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ) included.

The hydrogen peroxide may also be used in the form of its attachment compounds to solid supports, preferably hydrogen peroxide itself is used. The hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, used.

Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is on the one hand by the legal requirements and on the other hand determined by the desired effect; preferably 6-12% solutions in water are used.

For a color change by means of brightening or equation of the substrate, for example the hair, in addition to the oxidizing agents, at least one bleach booster is preferably used in the cosmetic compositions according to the invention.

• (BV-i) Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, und/oder
• (BV-ii) Carbonatsalze und/oder Hydrogencarbonatsalze, und/oder
• (BV-iii) organische Carbonate, und/oder
• (BV-iv) Carbonsäuren, und/oder
• (BV-v) Peroxoverbindungen.

Bleach boosters are preferably used to increase the bleaching action of the oxidizing agent, in particular the hydrogen peroxide. Suitable bleach boosters are

• (BV-i) compounds which give aliphatic peroxycarboxylic acids and / or optionally substituted perbenzoic acid under perhydrolysis conditions, and / or
• (BV-ii) carbonate salts and / or bicarbonate salts, and / or
• (BV-iii) organic carbonates, and / or
• (BV-iv) carboxylic acids, and / or
• (BV-v) Peroxo compounds.

As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry oxygen- and / or nitrogen-bonded acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

The carbonate or bicarbonate salts are preferably selected from at least one compound of the group consisting of ammonium, alkali (especially sodium and potassium), and alkaline earth (especially calcium), carbonate salts and bicarbonate salts. Particularly preferred carbonate or bicarbonate salts are ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, disodium carbonate, potassium bicarbonate, dipotassium carbonate and calcium carbonate. These particularly preferred salts can be used alone or in their mixtures of at least two representatives as bleaching amplifiers.

Preferably usable organic carbonates are selected from at least one compound of the group of carbonic acid monoesters and / or from at least one compound of the group of carbonic acid monoamides.

in der R für einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest, oder eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.Preferably usable carbonic acid monoesters are the carbonic acid monoesters of the formula (BV-1),

in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (BV-1), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Compositions particularly preferably used according to the invention are characterized in that the radical R in formula (BV-1) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert Butyl and hydroxymethyl and hydroxyethyl radicals.

in der R für einen gesättigten oder ungesättigten, geradkettigen, verzweigten, oder cyclischen, substituierten oder unsubstituierten Kohlenwasserstoffrest, oder eine substituierte oder unsubstituierte Arylgruppe bzw. einen substituierten oder unsubstituierten Heterocyclus steht.Preferred carbonic acid monoamides are the compounds of the formula (BV-2),

in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (BV-2), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Bleach enhancers of the formula (BV-2) which are particularly preferred according to the invention are characterized in that the radical R in formula (BV-2) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, Iso-butyl, tert-butyl and hydroxymethyl and hydroxyethyl radicals.

The acidic H atom of the carbonic acid monoester or monoamide can also be present in neutralized form, i. H. salts of carbonic acid monoesters or carbonic acid monoamides can also be used according to the invention. Carbonic acid monoesters or the carbonic acid monoamides which are present in completely or partially neutralized form, preferably in the form of the alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt, are preferred according to the invention.

As the bleach-enhancing carboxylic acid, in the compositions of the present invention, at least one compound selected from the group consisting of acetic acid, lactic acid, tartaric acid, citric acid, salicylic acid and orthophthalic acid may preferably be contained.

Bleach boosters are preferably peroxo compounds, in particular inorganic peroxo compounds. Among the bleach-enhancing peroxy compounds according to the invention there are no addition products of hydrogen peroxide to other components and also not hydrogen peroxide itself. Moreover, the choice of peroxo compounds is subject to no restrictions. Preferred peroxo compounds are peroxydisulfate salts, persulfate salts, peroxydiphosphate salts (especially ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, potassium peroxydiphosphate) and peroxides (such as barium peroxide and magnesium peroxide). Among these peroxo compounds which can also be used in combination, according to the invention, the peroxydisulfates, in particular ammonium peroxydisulfate, are preferred. Here, agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are preferred, which additionally comprise 0.01 to 2% by weight of at least one solid peroxo compound selected from ammonium, alkali metal and alkaline earth metal persulphates, peroxomonosulphates and peroxydisulphates preferred agents include peroxydisulfates, which are preferably selected from sodium peroxydisulfate and / or potassium peroxodisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxydisulfates.

Particular preference is furthermore given to persulfates, in particular the mixture of potassium peroxosulfate, potassium hydrogen sulfate and potassium sulfate, referred to as Caro's salt.

The bleach boosters are contained in the cosmetic agents according to the invention preferably in amounts of from 5 to 30% by weight, in particular in amounts of from 8 to 20% by weight, based in each case on the weight of the ready-to-use agent.

Furthermore, it has proved to be advantageous if the dyeing and / or brightening agents according to the invention contain nonionic surfactants.

Such surfactants having an HLB of 5.0 and greater are preferred. For the definition of the HLB value, express reference is made to the remarks in Hugo Janistyn, Handbook of Cosmetics and Fragrances, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Publishing Company mb H. Stuttgart, 1974, pages 466-474 , as well as the original works cited therein.

Particularly preferred non-ionic surface-active substances are substances that are commercially available as solids or liquids in pure form because of their ease of processing. The definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to natural-based products, mixtures of different homologs can be used, for example, with different alkyl chain lengths, such as those obtained with products based on natural fats and oils. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present. The term purity in this context refers rather to the fact that the chosen substances should preferably be free from solvents, stabilizers and other impurities.

• – alkoxylierte Fettalkohole mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettalkylgruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettalkylgruppen sind beispielsweise Lauryl-, Myristyl-, Cetyl-, aber auch Stearyl-, Isostearyl- und Oleylgruppen. Besonders bevorzugte Verbindungen dieser Klasse sind beispielsweise Laurylalkohol mit 2 bis 4 Ethylenoxid-Einheiten, Oleyl- und Cetylalkohol mit jeweils 5 bis 10 Ethylenoxideinheiten, Cetyl- und Stearylalkohol sowie deren Mischungen mit 10 bis 30 Ethylenoxideinheiten sowie das Handelsprodukt Aethoxal^® B (Henkel), ein Laurylalkohol mit jeweils 5 Ethylenoxid- und Propylenoxideinheiten. Neben den üblichen alkoxylierten Fettalkoholen können auch sogenannte „endgruppenverschlossene” Verbindungen erfindungsgemäß eingesetzt werden. Bei diesen Verbindungen weist die Alkoxygruppe am Ende keine OH-Gruppe auf, sondern ist in Form eines Ethers, insbesondere eines C1-C4-Alkyl-Ethers, „verschlossen”. Ein Beispiel für eine solche Verbindung ist das Handelsprodukt Dehypon^® LT 054, ein C_12-18-Fettalkoholol + 4,5 Ethylenoxid-butylether.
• – alkoxylierte Fettsäuren mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettsäuregruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettsäuren sind beispielsweise Laurin-, Myristin-, Palmitin-, Stearin-, Isostearin- und Ölsäure.
• – alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride. Beispiele für bevorzugte Verbindungen sind Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid.
• – Polyglycerinester und alkoxylierte Polyglycerinester. Bevorzugte Verbindungen dieser Klasse sind beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lameform^® TGI (Henkel)) und Poly(2)glycerinpolyhydroxystearat (Handelsprodukt: Dehymuls^® PGPH (Henkel)).
• – Sorbitan-Fettsäureester und alkoxylierte Sorbitan-Fettsäureester wie beispielsweise Sorbitanmonolaurat und Sorbitanmonolaurat + 20 Ethylenoxid (EO).
• – Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21, insbesondere 6 bis 15, Kohlenstoffatomen in der Alkylkette und 0 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beipielsweise Nonylphenol + 4 EO, Nonylphenol + 9 EO, Octylphenol + 3 EO und Octylphenol + 8 EO.

Preferred nonionic surfactants are

• - Alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ^® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, so-called "end-capped" compounds can also be used according to the invention. In these compounds, the alkoxy group at the end of no OH group, but is in the form of an ether, in particular a C1-C4-alkyl ether, "closed". An example of such a compound is the commercially available product ^® Dehypon LT 054, a C _12-18 -Fettalkoholol + 4.5 ethylene oxide-butyl ether.
• - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.
• - alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides. Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.
• Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxystearat (commercial product: Dehymuls ^® PGPH (Henkel)).
• Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.

Particularly preferred classes of nonionic surfactants are the alkoxylated fatty alcohols, the alkoxylated fatty acids and the alkylphenols and alkylphenol alkoxylates.

Agents according to the invention which contain non-ionic surface-active substances in quantities of 1-5% by weight have proved to be particularly advantageous.

Furthermore, the dyeing and / or brightening agents according to the invention may contain all known in such preparations active ingredients, additives and excipients. In many cases, the agents contain 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 to select the surfactants from anionic, cationic or nonionic surfactants. Anionic surfactants may be very particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C ₁₂ H ₂₅ - (C ₂ H ₄ O) ₆ -CH ₂ -COONa and in particular salts of saturated and especially unsaturated C 8 -C 22 -carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

These anionic surfactants should preferably be present in solid, in particular powder form. Very particular preference is given to solid soaps, especially sodium stearate, at room temperature. These are preferably present in amounts of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, before.

Suitable nonionic surfactants are in particular C 8 -C 22 -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Distearoylethylhydroxyethylammoniummethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ^® F 75 miles.

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

As a further constituent, the compositions according to the invention may contain at least one ammonium compound from the group of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of from 0.5 to 10, preferably from 1 to 5,% by weight, based on the total composition of the composition ,

• – 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 Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/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 Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – 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 Panthenol, Pantothensäure, 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, Brennnessel, 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, Fettalkohole und Fettsäureester,
• – 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 dyeing and / or brightening agents according to the invention may contain 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 such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers such as, for example, 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. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg 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 panthenol, pantothenic acid, 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, 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 alcohols and fatty acid esters,
• 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

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of the cosmetics, 2nd edition, Hüthig book publishing house, Heidelberg, 1989 , referenced.

The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents.

The compositions according to the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are for example creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also possible to provide a powdered or tablet-shaped formulation, which is preferred for dyeing and / or brightening agents.

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.

Preferred agents according to the invention are characterized in that they additionally contain a non-aqueous solvent, with particularly preferred agents according to the invention the solvent in a concentration of 0.1-30 weight percent, preferably in a concentration of 1-20 weight percent, most preferably in a concentration of 2-10 weight percent, each based on the agent.

In further preferred agents according to the invention the solvent is selected from ethanol, n-propanol, isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, phenoxyethanol and benzyl alcohol and their mixtures.

The pH of the compositions according to the invention can be adjusted within a wide range by suitable ingredients such as acidifying agent or alkalizing agent.

Oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen in the presence of oxidation dye precursors. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. Accordingly, the presence of oxidation dye precursors is not a mandatory requirement for the use of oxidizing agents in the compositions according to the invention. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.

According to the invention, however, the oxidation dye can also be applied together with a catalyst on the hair, the oxidation of the dye precursors, for. B. by atmospheric oxygen activated. Such catalysts are z. As 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 and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

• – 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 are z. As peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, for. B.

• - pyranose oxidase and z. 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.

In an application of oxidants, the actual colorant is conveniently prepared immediately prior to use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of formula (Ia) and optionally dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

In particular, in the case of hair that is difficult to dye, an agent according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After another period of exposure of 10 to 20 minutes is then rinsed and nachshampooniert if desired. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.

For the application of the compositions of the invention on the hair dyeing and / or brightening agents are mixed immediately before application with a hydrogen peroxide solution. The concentration of this hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6-12% solutions in water are used. The proportions of dyeing and / or lightening agent and hydrogen peroxide solution are usually in the range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution is particularly selected when no too pronounced Blondierwirkung is desired.

In addition, the compositions according to the invention may contain further ingredients. For example, use of certain metal ions or complexes may be preferred to obtain intense colorations. Agents according to the invention which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions are preferred here.

Preferred agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers additionally comprise Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, preferred agents being from 0.0001 to 2.5% by weight .-%, preferably 0.001 to 1 wt .-% of at least one compound from the group copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt ( II) chloride, cerium sulfate, cerium chloride, vanadium sulfate, manganese dioxide (MnO ₂ ).

Also preferred according to the invention is the use of so-called complexing agents. Complex images are substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents, ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Customary and preferred chelate complex images in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also, complex-forming polymers, ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms usually with the formation of chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine.

In the context of the present invention, it is particularly preferable to use one or more chelating agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (β-hydroxyethyl) glycine, N- (1,2-dicarboxy 2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Also to be mentioned as further preferred complexing polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

Further suitable complexing agents are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Another class of substances with complex-forming properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The complexing agent used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. These substances will be described below.

Compounds which are preferred according to the invention are phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or diethylenetriamine pentamethylenephosphonate (DTPMP ) or its hepta- or octasodium salt.

• (a) Nitrilotriessigsäure (NTA),
• (b) Diethylenetriaminpentaesigsäure (DTPA),
• (c) Ethylendiamindibernsteinsäure (EDDS),
• (d) Ethylenediamindiglutarsäure (EDGA),
• (e) 2-Hydroxypropylendiamindibernsteinsäure (HPDS),
• (f) Glycinamid-N,N'-dibernsteinsäure (GADS),
• (g) Ethylendiamin-N-N'-diglutarsäure (EDDG),
• (h) 2-Hydroxypropylendiamin-N-N'-dibernsteinsäure (HPDDS),
• (i) Ethylendiamintetraessigsäure (EDTA),
• (j) Ethylendicysteinsäure (EDC),
• (k) Diaminoalkyldi(sulfobernsteinsäure) (DDS),
• (l) Ethylendiamine-N-N'-bis(ortho-hydroxyphenylesigsäure (EDDHA),
• (m) N-2-hydroxyethyl-N,N-diessigsäure,
• (n) Glyceryliminodiessigsäure,
• (o) Iminodiessigsäure-N-2-hydroxypropylsulfonsäure,
• (p) Asparaginsäure-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonsäure,
• (q) 8-Alanin-N,N'-diessigsäure,
• (r) Asparaginsäure-N,N'-diessigsäure,
• (s) Asparaginsäure-N-monoessigsäure,
• (t) Dipicolinsäure,
• (u) sowie deren Salze und/oder Derivate

Particularly preferred agents according to the invention contain one or more substances from the group

• (a) nitrilotriacetic acid (NTA),
• (b) diethylenetriaminepentaacetic acid (DTPA),
• (c) ethylenediamine disuccinic acid (EDDS),
• (d) ethylenediamine-diglutaric acid (EDGA),
• (e) 2-hydroxypropylenediamine disuccinic acid (HPDS),
• (f) glycinamide-N, N'-disuccinic acid (GADS),
• (g) ethylenediamine-N-N'-diglutaric acid (EDDG),
• (h) 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS),
• (i) ethylenediaminetetraacetic acid (EDTA),
• (j) ethylene dicysteic acid (EDC),
• (k) diaminoalkyldi (sulfosuccinic acid) (DDS),
• (l) ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA),
• (m) N-2-hydroxyethyl-N, N-diacetic acid,
• (n) glyceryliminodiacetic acid,
• (o) iminodiacetic acid N-2-hydroxypropylsulfonic acid,
• (p) aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid,
• (q) 8-alanine-N, N'-diacetic acid,
• (r) aspartic acid-N, N'-diacetic acid,
• (s) aspartic acid N-monoacetic acid,
• (t) dipicolinic acid,
• (u) and their salts and / or derivatives

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine,

wobei bevorzugte Mittel Phosphonate, vorzugsweise Hydroxyalkan- bzw. Aminoalkanphosphonate und insbesondere 1-Hydroxyethan-1,1-diphosphonat (HEDP) bzw. dessen Di- oder Tetranatriumsalz und/oder Ethylendiamintetramethylenphosphonat (EDTMP) bzw. dessen Hexanatriumsalz und/oder Diethylentriaminpentamethylenphosphonat (DTPMP) bzw. dessen Hepta- oder Octanatriumsalz, enthalten.From the above-mentioned groups of substances, some representatives are particularly preferred in the context of the present invention. Particularly preferred according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers additionally contain one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins,

preferred agents being phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and especially 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP) or its hexasodium salt and / or diethylene triamine pentamethylene phosphonate (DTPMP) or its hepta- or octa-sodium salt.

Preferred agents according to the invention are formulated with little or no water. Particularly preferred agents according to the invention are characterized in that they contain less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight and in particular less than 0.5% by weight of water, preferred agents being anhydrous. The water content of the agent can be determined, for example, by means of titration according to Karl Fischer.

• – gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann
• – ein Mittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird,
• – dieses Mittel 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 oder M3 ein erfindungsgemäßes Mittel ist.

A second object of the present invention is a process for dyeing and optionally simultaneously whitening keratin fibers, in particular human hair, in which

• - If desired, a pretreatment agent M1 is applied to the fiber, then
• A means M2 is applied to the fiber, wherein, if desired, an additional agent M3 is added to the agent M2 before use,
• - This agent 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 means M1, M2 or M3 is an inventive means.

The agents according to the invention can accordingly be formulated as single-component agents (dyeing and whitening agents M2 or aftertreatment agents M4), as two-component agents (M2 + M3) or as three-component agents (M2 + M3 + M4) and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared are; the agent to be used is produced in such systems by the consumer directly before use by mixing the components.

A dyeing and whitening process in which the whitening cream and the oxidizing agent are initially present separately is preferred. A further subject of the present invention is therefore a process for dyeing and lightening human hair, in which an aqueous-based composition containing hydrogen peroxide is mixed with an agent according to the invention to form a homogeneous composition and applied to the hair.

In preferred processes of this type according to the invention, the aqueous composition contains from 1 to 20% by weight, preferably from 2 to 10% by weight and in particular from 3 to 6% by weight of hydrogen peroxide, calculated as 100% H _2, by weight O ₂ .

Further preferred processes of this kind according to the invention are characterized in that the aqueous-based composition comprising hydrogen peroxide is mixed with an agent according to the invention in a weight ratio of 1: 5 to 10: 1, preferably 1: 2 to 5: 1 and in particular 1: 2 to 2: 1 mixed into a homogeneous composition, and this is applied to the hair.

Alternatively, as mentioned above, a three-component system may also be used. reach. A further subject matter of the present invention is therefore a process for dyeing and lightening human hair which comprises an aqueous-based composition containing hydrogen peroxide with a further agent containing preferably at least one alkalinity donor and / or substantive hair dye and / or at least one oxidation dye precursor, and a composition according to the invention mixed to a homogeneous composition, and this is applied to the hair.

With regard to further preferred embodiments of the method according to the invention, mutatis mutandis the statements made concerning the agents according to the invention apply.

It is particularly preferred to support the coloration by physical measures. Processes according to the invention in which the application is assisted by the action of heat and / or UV radiation during the exposure time are preferred embodiments of the present invention.

The compounds of the general formula (I) are very suitable as direct drawers for hair coloring. In dyeings extremely intense shades with very good fastness properties, especially in the yellow, Ornage-, red, purple, blue and brown area are obtained. The Direktzieher also provide with the simultaneous use of oxidizing agents such as hydrogen peroxide or a mixture of hydrogen peroxide and peroxydisulfates bright nuances without attenuation of color intensity and color brilliance. In this way, the simultaneous lightening and coloring of hair is possible, which also on dark hair, a bright color can be achieved.

in der
CHR für einen Chromophor steht, der ausgewählt ist aus Anthrachinonfarbstoffen, Azofarbstoffen, Naphthochinonfarbstoffen, Triarylmethan-farbstoffen, Nitrophenylendiaminfarbstoffen, Nitroaminophenolfarbstoffen, Phenazinfarbstoffen, Oxazinfarbstoffen oder Thiazinfarbstoffen
L stellt eine Linker-Gruppierung dar, ausgewählt aus Strukturen der Formeln (II) bis (VII)

wobei n und m hierbei unabhängig voneinander eine ganze Zahl von 2 bis 6 darstellen und der Rest R1 für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe steht, und
wobei die Bindung zwischen Chromophor und Linker über ein am Chromophor vorhandenes Kohlenstoffatom, Stickstoffatom, Sauerstoffatom oder Schwefelatom erfolgt,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, Sulfat, p-Benzolsulfonat, p-Toluolsulfonat, Acetat, Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat
in Mitteln zum Färben und gegebenenfalls gleichzeitigen Aufhellen keratinischer Fasern.Another object of the present invention is therefore the use of cationic compounds of the formula (I):

in the
CHR is a chromophore selected from anthraquinone dyes, azo dyes, naphthoquinone dyes, triarylmethane dyes, nitrophenylenediamine dyes, nitroaminophenol dyes, phenazine dyes, oxazine dyes or thiazine dyes
L represents a linker moiety selected from structures of formulas (II) to (VII)

where n and m independently of one another represent an integer from 2 to 6 and the radical R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group , and
the bond between the chromophore and the linker being via a carbon atom, nitrogen atom, oxygen atom or sulfur atom present on the chromophore,
X ^- is a monovalent anion, preferably halide, hydrogen sulfate, sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate
in agents for dyeing and, if appropriate, simultaneous lightening of keratinic fibers.

• – Steigerung der Echtheitseigenschaften der Färbungen und/oder
• – Steigerung der Farbbrillanz und/oder
• – Steigerung der Hautverträglichkeit von Färbe bzw. Aufhellmitteln.

Particularly preferably, the use of the compounds serves to achieve certain advantageous effects. Preferred according to the invention are uses for

• Increasing the fastness properties of the dyeings and / or
• - Increase color brilliance and / or
• - Increase the skin compatibility of dye or brightening agents.

With regard to further preferred uses according to the invention, the mutated mutandis applies to the preferred agents.

in der
CHR für einen Chromophor steht, der ausgewählt ist aus Anthrachinonfarbstoffen, Azofarbstoffen, Naphthochinonfarbstoffen, Triarylmethan-farbstoffen, Nitrophenylendiaminfarbstoffen, Nitroaminophenolfarbstoffen, Phenazinfarbstoffen, Oxazinfarbstoffen oder Thiazinfarbstoffen
L stellt eine Linker-Gruppierung dar, ausgewählt aus Strukturen der Formeln (II) bis (VII)

wobei n und m hierbei unabhängig voneinander eine ganze Zahl von 2 bis 6 dar stellen und der Rest R1 für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe steht, und
wobei die Bindung zwischen Chromophor und Linker über ein am Chromophor vorhandenes Kohlenstoffatom, Stickstoffatom, Sauerstoffatom oder Schwefelatom erfolgt,
X^– steht für ein einwertiges Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, p-Benzolsulfonat, p-Toluolsulfonat, Acetat, Tetrafluoroborat, Trifluormethansulfonat, Hexafluorophosphat, Methansulfat oder Methansulfonat.Some of the cationic compounds contained in the agents according to the invention are not yet known. A further subject of the present invention are therefore cationic compounds of the formula (I):

in the
CHR is a chromophore selected from anthraquinone dyes, azo dyes, naphthoquinone dyes, triarylmethane dyes, nitrophenylenediamine dyes, nitroaminophenol dyes, phenazine dyes, oxazine dyes or thiazine dyes
L represents a linker moiety selected from structures of formulas (II) to (VII)

where n and m independently of one another represent an integer from 2 to 6 and the radical R ₁ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group stands, and
the bond between the chromophore and the linker being via a carbon atom, nitrogen atom, oxygen atom or sulfur atom present on the chromophore,
X ^- represents a monovalent anion, preferably halide, hydrogen sulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate.

• – Salze des 3-[(4-Amino-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-3-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 3-[(4-Amino-2-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]propanaminiums
  
• – Salze des 2-[(4-Amino-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-3-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-2-brom-9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{methyl[4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{ethyl[4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{methyl[3-methyl-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{ethyl[3-methyl-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{methyl[3-chlor-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{ethyl[3-chlor-4-(1,3-thiazol-2-yldiazenyl)phenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-methyl-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{3-methyl-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-chlor-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{3-chlor-4-[(5-nitro-1,3-thiazol-2-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-methyl-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethy-2-(ethyl{3-methyl-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(methyl{3-chlor-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-(ethyl{3-chlor-4-[(3-phenyl-1,2,4-thiadiazol-5-yl)diazenyl]phenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-2-nitrophenyl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des 2-[(4-Amino-3-nitrophenyl)amino]-N,N-dimethyl-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(methylamino)-2-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(methylamino)-3-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(dimethylamino)-2-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-{[4-(dimethylamino)-3-nitrophenyl]amino}-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[(2-hydroxyethyl)amino]-2-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[(2-hydroxyethyl)amino]-3-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[bis(2-hydroxyethyl)amino]-2-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  
• – Salze des N,N-Dimethyl-2-({4-[bis(2-hydroxyethylamino]-3-nitrophenyl}amino)-N-[(2-oxo-1,3-dioxolan-4-yl)methyl]ethanaminiums
  

Furthermore, the following compounds are not known from the literature and subject of the present invention

• Salts of 3 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane 4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-3-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 3 - [(4-amino-2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums
  
• Salts of 2 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-3-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {methyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {ethyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {methyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1,3-dioxolane-4 -yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {ethyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1,3-dioxolane-4 -yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {methyl [3-chloro-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- {ethyl [3-chloro-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3 dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3 dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-chloro-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-methyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-methyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) -diazenyl] -phenyl} -amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2- (ethyl {3-chloro-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) -diazenyl] -phenyl} -amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of 2 - [(4-amino-2-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of 2 - [(4-amino-3-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - {[4- (methylamino) -2-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanamine
  
• Salts of N, N-dimethyl-2 - {[4- (methylamino) -3-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - {[4- (dimethylamino) -2-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - {[4- (dimethylamino) -3-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium
  
• Salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums
  
• Salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino] -3-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums
  
• Salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  
• Salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethylamino] -3-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums
  

Examples

1 Synthesis Examples:

Synthesis Example 1: Synthesis of 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo) 1,3-dioxolan-4-yl) methyl] propanaminium p-toluenesulfonate (DZ1)

1.1. Synthesis of 4 - ({[(4-methylphenyl) sulfonyl] oxy} methyl) 1,3-dioxolan-2-one

45.6 g (0.24 mol) of p-toluenesulfonyl chloride were dissolved in 100 ml of tetrahydrofuran (abs.). There were added 30.6 g (0.30 mol) of triethylamine and the reaction cooled to 0 ° C. Then 23.6 g (0.20 mol) of glycerol carbonate (4- (hydroxymethyl) -1,3-dioxolan-2-one) were added dropwise dissolved in 100 ml of tetrahydrofuran (abs.). It was stirred for 8 hours at 0 ° C, then allowed to come the reaction mixture to room temperature and stirred for a further 12 hours at room temperature. The reaction solution was diluted with 1.0 L of ethyl acetate and washed with water. It was then washed first with 0.2 M aqueous hydrochloric acid solution, then with saturated sodium bicarbonate solution. The organic phase was dried with sodium sulfate and then concentrated completely on a rotary evaporator.
Yield: 50.7 g (98.3%)

1.2. Synthesis of 1-amino-4 - {[3- (dimethylamino) propyl] amino} -2-methyl-9,10-anthraquinone

25.0 g (0.08 mol) of 1-amino-4-bromo-2-methylanthraquinone and 81.0 g (0.80 mol) of 3- (dimethylamino) propylamine were dissolved in 200 ml of N-methylpyrrolidone for 18 hours at 80 ° C stirred. After completion of the reaction, the reaction mixture was allowed to cool. Thereafter, it was poured onto 1000 ml of water. The resulting dark blue solid was filtered off and washed with water. The product was dissolved in 200 ml of 10% aqueous hydrochloric acid solution. After filtration, the filtrate was brought to pH 8 by the addition of a 10 M aqueous sodium hydroxide solution. This solution was placed in the refrigerator overnight. The precipitated solid was filtered off again and dried in vacuo.
Yield: 8.9 g (32.2%)

1.3. Synthesis of 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3 -dioxolan-4-yl) methyl] propanaminium p-toluenesulfonate (DZ1)

8.9 g (26.3 mmol) of 1-amino-4 - {[3- (dimethylamino) propyl] amino} -2-methyl-9,10-anthraquinone from stage 1.2. were combined with 7.5 g (28.9 mmol) of 4- ({[(4-methylphenyl) sulfonyl] oxy} methyl) 1,3-dioxolan-2-one from step 1.1. heated in 200 ml of toluene for 5 hours under reflux. After cooling, the precipitated solid was filtered off and washed with toluene. The product was obtained in the form of a dark blue powder.
Yield: 3.8 g (23.5%)

2 coloration examples:

2.1 Preparation of the coloring creams

The following coloring creams were prepared: 2.1.1 Nonionic coloring cream Hydrenol ^® D 6.0 g Lorol ^® (technical) 6.0 g Eumulgin ^® RH 40 1.0 g Eumulgin ^® B1 3.0 g Eumulgin ^® B2 3.0 g PHB Methylester 0.3 g PHB propyl 0.2 g phenoxyethanol 1.0 g Polydiol ^® 400 5.0 g direct Dyes 1.0 g ammonium sulfate 1.0 g (in 30.0 g of water) Natrosol ^® 250 HR 1.0 g (in 15.0 g of water) NaOH 0.1% pH value adjustment water ad 100 g

The first nine components were melted together at 80 ° C, after which the dye was added. This mixture was emulsified with a solution of the ammonium sulfate in 30 g of water. Then, a swelling of 1.0 g Natrosol 250 HR ^® was added in 15.0 grams of water. The pH stated in Table 2 was adjusted with 0.1% sodium hydroxide solution, then made up to 100 g with water. 2.1.2 Cationic Dyeing Cream Stenol ^® 16/18 4.0 g Eumulgin ^® B1 1.0 g Dehyquart® ^® A-CA 2.0 g ammonium sulfate 1.0 g (in 30.0 g of water) direct Dyes 1.0 g water at 100 g

The Stenol ^® 16/18 was melted together with Eumulgin ^® B1 and Dehyquart ^® A-CA, the melt was then emulsified with hot water. Then, the dye and the aqueous ammonium sulfate solution were added. The pH was with ammonia bwz. Citric acid was adjusted to the value given in the table, then it was made up to 100 g with water. 2.1.3 Anionic dye cream Hydrenol ^® D 1.0 g Lorol® ^® techn. 1.0 g Akypo Soft ^® RLM 45N 1.1 g PHB propyl 0.1 g PHB Methylester 0.1 g ammonium sulfate 1.0 g (in 30.0 g of water) Direct drawers DZ 1.0 g water at 100 g

The first five components were melted together. This melt was emulsified with hot water, then the water-dissolved or predispersed dye was added and the ammonium sulfate solution was added. The pH indicated in the table was adjusted with ammonia or citric acid, then made up to 100 g with water. 2.2 List of raw materials used Akypo RLM 45 NV ^® Lauryl alcohol 4.5 EO acetic acid sodium salt (at least 22% active ingredient content, INCI name: sodium laureth-5 carboxylates) (Chem-Y) Dehyquart® ^® A-CA Trimethylhexadecylammonium chloride (about 24-26% active ingredient, INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis) Eumulgin ^® B 1 Cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis) Eumulgin ^® B2 Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) Eumulgin ^® RH 40 hardened castor oil with approx. 40 EO units (INCI name: PEG-40 Hydrogenated Castor Oil) (Cognis) Hydrenol ^® D C _16-18 fatty alcohol (INCI name: Cetearyl acohol) (Cognis) Lorol (techn.) ^® C _12-18 fatty alcohol (INCI name: Coconut Alcohol) (Cognis) Natrosol ^® 250 HR Hydroxyethylcellulose (INCI name: Hydroxyethylcellulose) (Hercules) Polydiol ^® 400 Polyethylene glycol (INCI name: PEG-8) (Cognis) Stenol ^® 1618 C _16-18 fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis)

2.3 colorations

Each 1.8 g of the dyeing cream were applied to an approximately 6 cm long strand of human hair (Kerling Euronaturhaar, blond) and left there for 30 minutes at 30 ° C. After completion of the exposure time, the hair was rinsed, washed with a conventional shampoo and then dried. The hair tresses were dyed in the shades indicated in Table 2. DZ1: 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3 dioxolan-4-yl) methyl] propanaminium p-toluenesulfonate dye coloring cream PH value Color nuance (intensity) DZ 1 1 7.0 gray blue (++) DZ 1 1 9.0 gray blue (++) DZ 1 2 7.0 deep blue (+++) DZ 1 2 9.0 deep blue (+++) DZ 1 3 7.0 smoke blue (++) DZ 1 3 9.0 smoke blue (++) Intensity: + = low, ++ = medium, +++ = high

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 998908 A2 [0134]

Cited non-patent literature

• Hugo Janistyn, Handbook of Cosmetics and Fragrances, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 [0200]
• Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Publishing Company mb H. Stuttgart, 1974, pages 466-474 [0200]
• Kh. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Buch Verlag, Heidelberg, 1989 [0215]

Claims (16)

Agent for dyeing and optionally simultaneous whitening of keratin fibers, in particular human hair, containing at least one cationic compound of the formula (I):

in which CHR is a chromophore selected from anthraquinone dyes, azo dyes, naphthoquinone dyes, triarylmethane dyes, nitrophenylenediamine dyes, nitroaminophenol dyes, phenazine dyes, oxazine dyes or thiazine dyes L represents a linker moiety selected from structures of formulas (II) to (VII )

where n and m independently of one another represent an integer from 2 to 6 and the radical R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group and wherein the bond between the chromophore and the linker is via a carbon atom, nitrogen atom, oxygen atom or sulfur atom present on the chromophore, X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, Tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate. An agent for dyeing and optionally simultaneously lightening keratinic fibers according to claim 1, characterized in that the compounds of the formula (I) have as chromophore CHR an anthraquinone dye which is preferably selected from structures of the formula (VIII)

in which R _{1 is} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group, R _2, R 3 independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkoxy group or a C ₁ -C ₆ alkyl group. Agent for dyeing and optionally simultaneous lightening of keratinic fibers according to one of claims 1 to 2, characterized in that it contains at least one cationic compound from the group of Salts of 3 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane 4-yl) methyl] propanaminiums Salts of 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums Salts of 3 - [(4-amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums Salts of 3 - [(4-amino-3-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums Salts of 3 - [(4-amino-2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] propanaminiums Salts of 2 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums Salts of 2 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums Salts of 2 - [(4-amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums Salts of 2 - [(4-amino-3-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums Salts of 2 - [(4-amino-2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1, 3-dioxolan-4-yl) methyl] ethanaminiums contains. An agent for dyeing and optionally simultaneous lightening of keratinic fibers according to any one of claims 1 to 3, characterized in that the compounds of formula (I) as chromophore CHR have an azo dye, which is preferably selected from structures of formula (IX)

in which A is a carbocyclic or heterocyclic, optionally substituted, uncharged ring system, R _{1 is} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group, R ₂ , R 3 independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkoxy group or a C ₁ -C ₆ -alkyl group. Agent for dyeing and, if appropriate, simultaneous lightening of keratinic fibers according to Claim 4, characterized in that the group A in formula (IX) represents an optionally substituted heterocycle, which is preferably selected from heterocycles of the formulas (X) to (XXI)

wherein the radicals R4 and R5 independently of one another represent a hydrogen atom, a nitro group, a nitro group, a halogen atom, a C ₁ -C ₆ -alkylsulfonyl group, a carbamoyl group, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -alkoxy group or a phenyl group. Agent for dyeing and optionally simultaneous lightening of keratinic fibers according to one of claims 1 to 5, characterized in that it contains at least one cationic compound from the group of Salts of N, N-dimethyl-2- {methyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- {ethyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- {methyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1,3-dioxolane-4 -yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- {ethyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1,3-dioxolane-4 -yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- {methyl [3-chloro-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- {ethyl [3-chloro-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} - N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (methyl {4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3 dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (ethyl {4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3 dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (methyl {3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (ethyl {3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (ethyl {3-chloro-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (methyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (ethyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (methyl {3-methyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (ethyl {3-methyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) -diazenyl] -phenyl} -amino) -N - [(2 oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (ethyl {3-chloro-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) -diazenyl] -phenyl} -amino) -N - [(2 -oxo-1,3-dioxolan-4-yl) methyl] ethanaminium. Agent for dyeing and, if appropriate, simultaneous lightening of keratinic fibers according to one of Claims 1 to 6, characterized in that the compounds of the formula (I) have as chromophore CHR a nitrophenylenediamine dye which is preferably selected from structures of the formula (XXII)

in which the radicals R _1, R ₁ 'and R ₁ "independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group. Agent for dyeing and optionally simultaneous lightening of keratinic fibers according to one of claims 1 to 6, characterized in that it comprises at least one cationic compound from the group of Salts of 2 - [(4-amino-2-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium Salts of 2 - [(4-amino-3-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium Salts of N, N-dimethyl-2 - {[4- (methylamino) -2-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanamine Salts of N, N-dimethyl-2 - {[4- (methylamino) -3-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium Salts of N, N-dimethyl-2 - {[4- (dimethylamino) -2-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium Salts of N, N-dimethyl-2 - {[4- (dimethylamino) -3-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium Salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums Salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino] -3-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums Salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethyl) amino] -3-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums contains. Agent for dyeing and, if appropriate, simultaneous lightening of keratinic fibers according to one of Claims 1 to 8, characterized in that it contains the compound (s) of the formula (I) in amounts of from 0.001 to 5% by weight, preferably from 0.0025 to 2 , 5 wt .-%, particularly preferably from 0.005 to 1.5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the total agent contains. Agent for dyeing and optionally simultaneous whitening of keratinic fibers according to any one of claims 1 to 9, characterized in that it additionally contains - based on its weight - from 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes. Agent for dyeing and, if appropriate, simultaneous lightening of keratinic fibers according to one of Claims 1 to 10, characterized in that it contains 0.5 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 2.5 to 10 Wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ) contains. Process for dyeing and, if appropriate, simultaneous lightening of keratin fibers, in particular human hair, characterized in that If desired, a pretreatment agent M1 is applied to the fiber, then an agent M2 is applied to the fiber, optionally adding to the agent M2 before use a further agent M3, this agent M2 after a time of 5-30 minutes is rinsed from the fiber - and after treatment optionally a post-treatment agent M4 applied to the fiber and rinsed after a contact time of a few minutes, wherein at least one of the means M1, M2 or M3 is an agent according to one of claims 1 to 11. Use of cationic compounds of the formula (I):

in which CHR is a chromophore selected from anthraquinone dyes, azo dyes, naphthoquinone dyes, triarylmethane dyes, nitrophenylenediamine dyes, nitroaminophenol dyes, phenazine dyes, oxazine dyes or thiazine dyes L represents a linker moiety selected from structures of formulas (II) to (VII )

where n and m independently of one another represent an integer from 2 to 6 and the radical R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group and wherein the bond between the chromophore and the linker is via a carbon atom, nitrogen atom, oxygen atom or sulfur atom present on the chromophore, X ^- is a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate, Tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate in agents for dyeing and optionally simultaneous whitening keratinic fibers. Use according to claim 14 for i. Increasing the fastness properties of the dyeings and / or ii. Increase color brilliance and / or iii. Increase the skin compatibility of dye or lightening agents. Cationic compounds of the formula (I):

in which CHR is a chromophore selected from anthraquinone dyes, azo dyes, naphthoquinone dyes, triarylmethane dyes, nitrophenylenediamine dyes, nitroaminophenol dyes, phenazine dyes, oxazine dyes or thiazine dyes L represents a linker moiety selected from structures of formulas (II) to (VII )

where n and m independently of one another represent an integer from 2 to 6 and the radical R ₁ represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group and wherein the bond between the chromophore and the linker is via a carbon atom, nitrogen atom, oxygen atom or sulfur atom present on the chromophore, X ^- represents a monovalent anion, preferably halide, hydrogensulfate, ½ sulfate, p-benzenesulfonate, p-toluenesulfonate, acetate , Tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate. Cationic compounds of the formula (I) according to Claim 16, selected from: salts of 3 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl N - [(2-oxo-1,3-dioxolan-4-yl) methyl] propanaminium salts of 3 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracene-1] yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] propanaminium salts of 3 - [(4-amino-2-methyl-9,10 dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] propanaminium salts of 3 - [( 4-amino-3-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl ) methyl] propanaminiumsalts of 3 - [(4-amino-2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2 oxo-1,3-dioxolan-4-yl) methyl] propanaminiums Salts of 2 - [(4-amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminium salts of 2 - [(4-amino-3-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N- [ (2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of 2 - [(4-amino-2-methyl-9,10-dioxo-9,10-dihydroanthracen-1-yl) -amino ] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of 2 - [(4-amino-3-bromo-9,10-dioxo) 9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of 2 - [(4-amino -2-bromo-9,10-dioxo-9,10-dihydroanthracen-1-yl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- {methyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N - [(2-oxo-1,3-dioxolan-4-yl) Methyl] ethanaminiums - salts of N, N-dimethyl-2- {ethyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N - [(2-oxo-1,3-dioxolane-4 -yl) methyl] ethanaminiumsalts of N, N-dimethyl-2- {methyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- {ethyl [3-methyl-4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} -N- (2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- {methyl [3-chloro-4- (1,3-thiazol-2-yldiazenyl) phenyl ] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- {ethyl [3-chloro-4- (1,3-) thiazol-2-yldiazenyl) phenyl] amino} -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- (methyl {4 - [( 5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl -2- (ethyl {4 - [(5-nitro-1,3-Thiaz ol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- (methyl {3- Methyl 4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of the N, N-dimethyl-2- (ethyl {3-methyl-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) - N - [(2-oxo-1 , 3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- (ethyl {3-chloro-4 - [(5- nitro-1,3-thiazol-2-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2 - (methyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums - salts of N, N-dimethyl-2- (ethyl {4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo -1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- (methyl {3-met hyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminiums Salts of N, N-dimethyl-2- (ethyl {3-methyl-4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) -diazenyl] -phenyl} -amino) -N - [(2 -oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- (methyl {3-chloro-4 - [(3-phenyl-1,2,4-thiadiazole) 5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- (ethyl {3-chloro) 4 - [(3-phenyl-1,2,4-thiadiazol-5-yl) diazenyl] phenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of the 2 - [(4-amino-2-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of 2 - [( 4-amino-3-nitrophenyl) amino] -N, N-dimethyl-N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2- { [4- (methylamino) -2-nitrophenyl] amino} -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2 - {[4- (methylamino) -3-nitrophenyl] amino} -N - [(2-oxo-1,3-dioxolan-4 -yl) methyl] ethanaminiums - salts of N, N-dimethyl-2 - {[4- (dimethylamino) -2-nitrophenyl] amino} -N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanaminium salts of N, N-dimethyl-2 - {[4- (dimethylamino) -3-nitrophenyl] amino} - N - [(2-oxo-1,3-dioxolan-4-yl) methyl] ethanamine - Salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl) methyl ] ethanaminiums - salts of N, N-dimethyl-2 - ({4 - [(2-hydroxyethyl) amino] -3-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolan-4-yl ) methyl] ethanaminium salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethyl) amino] -2-nitrophenyl} amino) -N - [(2-oxo-1,3-dioxolane 4-yl) methyl] ethanaminium salts of N, N-dimethyl-2 - ({4- [bis (2-hydroxyethyl) amino] -3-nitrophenyl} amino) -N - [(2-oxo-1,3 dioxolan-4-yl) methyl] ethanaminiums.