WO2010034626A2 - Novel developer components - Google Patents

Abstract

The present invention relates to means for dying keratin fibers, particularly human hair, which contain at least one p-phenylenediamine derivative of the formula (I) as a developer component in a cosmetically acceptable carrier, wherein the groups R1 and R2 stand independently of each other for a hydrogen atom, a hydroxyl group, a C₁-C₆ alkoxy group, a halogen atom, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₁-C₆ monohydroxyalkyl group, a C₂-C₆ polyhydroxyalkyl group, an aryl group, a heteroaryl group, or an amino group, the group A stands for a -CR2H- group, an oxygen atom, or an NR3 group, wherein R3 stands for a hydrogen atom, a C₁-C₆ alkyl group, a C₁-C₆ monohydroxyalkyl group, or a C₂-C₆ polyhydroxyalkyl group, and n stands for the number 1, 2, or 3.

Description

 N e u e t i n c e m e n t e n c e m e n t e n s "

The present invention relates to agents for coloring keratinic fibers containing specific tricyclic p-phenylenediamine derivatives, a process for dyeing hair with these agents, the use of these p-phenylenediamine derivatives in oxidative colorants and some of these compounds themselves.

For the dyeing of keratin fibers, in particular human hair, the so-called oxidation colorants play a preferred role because of their intense colors and good fastness properties. Such colorants 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 developer components are usually primary aromatic amines having a further, 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 ,

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-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2 -Hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -diaminopropan-2-ol.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used. Particularly suitable as coupler substances are 1-naphthol, 1, 5,7,7,7,7,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine and 1-phenyl 3-methyl-pyrazolone-5, 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 and 2-methyl-4-chloro-5-aminophenol. Good oxidation dye precursors are primarily intended to meet the following requirements: They must form the desired color shades in sufficient intensity and authenticity in the oxidative coupling. You must also have a good Aufziehvermögen on the fiber, especially in human hair no significant differences between strained and freshly regrowed hair may exist (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g.

Perm liquids. Finally, if applied as a hair dye, they should not stain the scalp too much and above all they should be safe in terms of toxicology and dermatology. Furthermore, the coloring obtained by bleaching should easily back from the Hair can be removed, if it does not correspond to the individual wishes of each person and should be reversed.

But with a developer component or a special coupler / developer combination, it is usually not possible to obtain a natural color shade on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used.

There is therefore a constant need for new, improved dye components which are unproblematic in terms of toxicology and dermatology.

Even if intensive and long-lasting dyeings are possible with the known compounds such as, for example, p-phenylenediamine and p-toluenediamine, these substances still still have an improvement potential, in particular with regard to their toxicological profile. However, the replacement compounds found in the search for substitutes for the above developers are often

Weaknesses in the application area. Especially the ability to gray cover the

Approach often does not meet the requirements of permanent hair dyes requirements.

The object of the present invention is therefore to find new developers for oxidative hair coloring with a toxicologically advantageous profile and good performance properties, in particular with regard to their gray coverage.

Surprisingly, it has now been found that special tricyclic p-phenylenediamine derivatives to

Developer components meet requirements in a high degree. The developer components according to the invention enable the production of rich and intense nuances, which are distinguished by a remarkable gray coverage.

A first subject of the present invention are therefore agents for coloring keratinic fibers, which in a cosmetically acceptable carrier as the developer component at least one p-

Phenylenediamine derivative of the formula (I)

wherein the radicals R 1 and R ₂ independently of one another represent a hydrogen atom, a hydroxy group, a C ₁ -C ₆ -alkoxy group, a halogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -monohydroxyalkyl group , a C ₂ -C ₆ polyhydroxyalkyl group, an aryl group, a heteroaryl group or an amino group, the radical A is a group -CR 2 H-, an oxygen atom or a grouping -NR 3 -, wherein R 3 is a hydrogen atom, a Ci-Cβ Alkyl group, a C ₁ -C ₆ monohydroxyalkyl group or a C ₂ -C ₆ polyhydroxyalkyl group, and n is either the number 1, 2 or 3. According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the oxidation dyes according to the invention are primarily suitable for dyeing keratin fibers, in principle, there is nothing to prevent their use in other fields, in particular in color photography.

Since the p-phenylenediamine derivatives according to the invention are amino compounds, the known acid addition salts can be prepared therefrom in the customary manner. All statements of this document and accordingly the scope claimed therefore relate both to the present in free form compounds as well as their physiologically acceptable salts of organic or inorganic acids. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred. Very particular preference according to the invention is given to the monohydrochlorides, the dihydrochloride and the trihydrochlorides. Salts are preferred in which the molar amount of the acid corresponds to the molar amount of the developer component or an integer multiple thereof. However, it is also erfindunsgemäß preferred if the molar amount of acid corresponds to 1, 5 times the molar amount of the developer component.

Examples of the C ₁ - to C ₆ -alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl , n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl and 2,2-dimethylbutyl. Ethyl and methyl are preferred alkyl groups. A preferred C ₁ to C ₆ alkenyl group is the allyl group. Preferred C ₁ to C ₆ alkoxy groups are the methoxy and ethoxy groups. Furthermore, as preferred examples of a C ₁ to C ₆ monohydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxy propyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₆ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here. The p-phenylenediamine derivatives of the formula (I) can be prepared by conventional organic methods. For example, reference is made at this point to the experimental procedures in the context of the embodiments.

Some of the p-phenylenediamine derivatives of the formula (I) which are now claimed as developer components have already been described in the literature, but references to their advantageous properties in the context of oxidative dyeing of keratinic fibers can not be found in these references.

In the context of the work on which this application is based, it has been shown that it is preferred that the radical R 1 is a hydrogen atom, a C ₁ -C ₆ -alkoxy group, a halogen atom, a C ₁ -C ₆ -alkyl group or a C ₁ -C ₆ monohydroxyalkyl group. Particular preference is given to compounds of the formula (I) in which R 1 is a hydrogen atom, a methyl group or a chlorine atom. Compounds of the formula (I) in which R 1 is a hydrogen atom are very particularly preferred according to the invention. In addition, compounds of the formula (I) have proved to be advantageous in terms of their application properties in which R 2 represents a hydrogen atom, a C 1 -C ₆ -alkyl group, a hydroxy group or a d-Ce-monohydroxyalkyl group. Particularly advantageous properties are exhibited by the compounds of the formula (I) in which the radical R 2 is a hydrogen atom, a hydroxyl group, a methyl group or a hydroxymethyl group. Compounds of the formula (I) in which R 2 is a hydrogen atom are very particularly preferred according to the invention. In addition, compounds of the formula (I) in which A is a group - CR 2 H- or an oxygen atom are preferred according to the invention.

In a first preferred embodiment of the present invention, compounds of the formula (I) have proven to be particularly preferred in which n is 1. Accordingly, in these compounds, the third ring is 5-membered.

Particularly preferred compounds of this embodiment of the present invention are: 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-7-amine

8-methyl-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazine-7-amine

8-chloro-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazine-7-amine 7-amino-2,3,3a, 4-tetrahydro 1 H-pyrrolo [2,1-c] [1,4] benzoxazin-1-ol 7-amino-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1, 4 ] benzoxazine-2-ol

7-amino-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-3-ol 1-methyl-2,3,3a, 4-tetrahydro 1 H-pyrrolo [2,1-c] [1,4] benzoxazine-7-amine. 2-Methyl-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4 ] benzoxazin-7-amine

3-methyl-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-7-amine (7-amino-2,3,3a, 4-tetrahydro -1 H -pyrrolo [2,1-c] [1,4] benzoxazin-1-yl) methanol (7-amino-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1, 4] benzoxazin-2-yl) methanol (7-amino-2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-3-yl) methanol

Within this group, the compound 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] - [1, 4] benzoxazine-7-amine as an explicitly very particularly preferred novel tricyclic p-phenylenediamine derivative is an outstanding Position.

In a second preferred embodiment of the present invention, compounds of the formula (I) have proved to be particularly advantageous in which n is 2. Accordingly, in this group of compounds, the third ring is 6-membered. Particularly preferred representatives of this embodiment of the present invention are:

6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine 2-methyl-6,6a, 7,8,9,10- hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine. 2-Chloro-6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4 ] benzoxazine-3-amine

3-Amino-6,6a, 7,8,9, 10-hexahydro-pyrido [2, 1-c] [1,4] benzoxazin-10-ol 3-amino-6,6a, 7,8,9 , 10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-9-ol 3-amino-6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [ 1, 4] benzoxazin-8-ol

3-Amino-6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-7-ol 10-methyl, 6,6a, 7,8,9 , 10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine 9-methyl, 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [ 1, 4] benzoxazin-3-amine 8-methyl, 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine 7-methyl, 6,6a, 7,8,9 , 10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine

- (3-Amino-6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-10-yl) methanol

- (3-Amino-6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-9-yl) -methanol (3-amino-6,6a, 7 , 8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-8-yl) -methanol (3-amino-6,6a, 7,8,9,10-hexahydro-pyrido [ 2,1-c] [1,4-benzoxazin-7-yl] -methanol 1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine 8-amine 9-methyl-1, 2,4a, 5-tetrahydro-4H- [1,4] -oxazino [3,4-c] [1,4] benzoxazine-8-amine;

- 9-chloro-1, 2,4a, 5-tetrahydro-4H- [1,4] -oxazino [3,4-c] [1,4] benzoxazine-8-amine

Within this group, the two compounds 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1, 4] benzoxazin-3-amine and 1, 2,4a, 5-tetrahydro- 4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine is particularly preferred.

If there are ambiguities with regard to the structures resulting from the designations of the inventively preferred compounds of the two embodiments, it is this

Make explicit reference to the relevant passages of the priority document.

The tricyclic compounds according to the invention each contain at least one carbon atom with four different substituents. Because of these stereogenic centers is in the substance group

Stereoisomerism possible. Stereoisomers are compounds which have the same constitution, but a different spatial, three-dimensional arrangement of their atoms and atomic groupings and are not to be made to coincide with each other.

If the stereoisomers behave like image and mirror image, they are referred to as enantiomers. Enantiomers of a compound can not be characterized by physical properties such as

Melting point, boiling point, refractive index, density, spectroscopic methods such as IR, UV or

Be differentiated by NMR spectroscopy or by their chemical reactivity towards achiral reactants.

If stereosiomers do not behave like image and mirror image, they are called diastereomers.

Diastereomers occur in compounds with more than one chiral element.

Diastereomeric structures can not be interconverted by any symmetry operation. They can be chiral or achiral, with a chiral diastereomer always being a corresponding one

Has an enantiomer, but not an achiral one. In contrast to enantiomers, diastereomers have different free standard formation enthalpies; They differ in their chemical, physical and spectroscopic properties and can therefore usually with

Standard procedures are separated.

For the designation of enantiomers and diastereomers, the absolute configuration of the

Chiralitätszentren determined under the aid of the Cahn-Ingold-Prelog rules and this by means of

Stereo descriptors R and S are described.

Enantiomerism or diastereomerism is also possible with the compounds according to the invention. In the course of the present invention, all enantiomers and the diastereomers of the Invention, ie both the R-enantiomer and the S-enantiomer and the S, S, R, R, S, R-,

R, S stereoisomers of each substance are in accordance with the invention.

Moreover, it is possible to use both an equimolar mixture of the stereoisomers (racemate) and

To use means for dyeing hair as well as any other conceivable molar ratio of the

Stereoisomers to use.

The following enantiomers have been found to be particularly preferred according to the invention:

- (3aR) -2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] - [1,4] benzoxazin-7-amine

- (3aS) -2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] - [1, 4] benzoxazine-7-amine

- (6aR) -6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine

- (6aS) -6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine

(4aR) -1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine and (4aS) -1, 2, 4a, 5-Tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine

In addition to the p-phenylenediamine derivatives of the formula (I), the colorants according to the invention may also contain at least one coupler component.

Coupler components according to the invention allow at least one substitution of a chemical

Remainder of the coupler due to 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 at least two groups on the cycle selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. When the cyclic connection is on

Six-membered ring (preferably aromatic), so said groups are preferably in the ortho position or meta position to each other.

Coupler components according to the invention are preferably selected from one of the following classes:

m-aminophenol and / or its derivatives,

m-diaminobenzene and / or its derivatives,

o-diaminobenzene and / or its derivatives,

o-aminophenol derivatives, such as o-aminophenol,

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.

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, S-trifluoroacetylamino ^ -chloro-θ-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 compounds mentioned above.

Particularly preferred m-diaminobenzene coupler components are selected from at least one

Compound from the group formed from m-phenylenediamine, 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-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-

Morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine, 1-amino-3-bis-

(2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of all the above

Links.

Particularly preferred o-diaminobenzene coupler components are selected from at least one

A compound from the group formed from 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all the above-mentioned compounds.

Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group which is formed from resorcinol, resorcinol monomethyl ether,

Methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and

1, 2,4-trihydroxybenzene.

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, 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.

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.

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, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 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'-bis) 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-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, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1, 2,4- Trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6 Dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1 , 7-Dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, A-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

In a further preferred embodiment, the colorants according to the invention contain at least one further developer component.

It may be preferred according to the invention to use as a further developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particularly preferred p-phenylenediamines 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, A-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-phenylenediamine, 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 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 , -p-phenylenediamine N-bis (.beta.-hydroxyethyl), 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, as well as the physiologically acceptable salts of these compounds.

It may further be preferred according to the invention to use as developer component compounds containing at least two aromatic nuclei which are reacted with amino and / or

Hydroxyl groups are substituted. In particular, preferred binuclear developer components are selected from at least one of the following compounds: N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propane-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 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 thereof

Links.

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.

Particularly preferred p-aminophenols are p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-ol 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, A-

Amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.

Very particularly preferred compounds 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.

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.

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.

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- (1 H -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, and the physiologically acceptable salts of these compounds. The following coupler / developer combinations have proved particularly suitable according to the invention:

2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-7-amine / 5-amino-2-methylphenol 2,3,3a, 4-tetrahydro -1 H-pyrrolo [2,1-c] - [1,4] benzoxazin-7-amine / 3-amino-2-chloro-6-methylphenol 2,3,3a, 4-tetrahydro-1H-pyrrolo [ 2,1-c] - [1,4] benzoxazin-7-amine / 2,4-dichloro-3-aminophenol

- 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] - [1,4] benzoxazine-7-amine / 2- (2,4-diaminophenoxy) ethanol

2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-7-amine / 1,3-bis (2,4-diaminophenoxy) propane 2,3 , 3a, 4-Tetrahydro-1H-pyrrolo [2,1-c] - [1,4] benzoxazin-7-amine / resorcinol

2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-7-amine / 2-methylresorcinol 2,3,3a, 4-tetrahydro-1H- pyrrolo [2,1-c] - [1,4] benzoxazin-7-amine / 2-amino-3-hydroxypyridine 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] - [ 1, 4] benzoxazin-7-amine / 3-amino-2-methylamino-6-methoxypyridine

2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazin-7-amine / 1-naphthol

- 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] - [1, 4] benzoxazine-7-amine / 1, 5-dihydroxynaphthalene 2,3,3a, 4-tetrahydro-1 H-pyrrolo [2,1-c] - [1,4] benzoxazine-7-amine / 2,7-dihydroxynaphthalene

- 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / 5-amino-2-methylphenol

6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine / 3-amino-2-chloro-6-methylphenol 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / 2,4-dichloro-3-aminophenol

- 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / 2- (2,4-diaminophenoxy) ethanol

6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine / 1,3-bis (2,4-diaminophenoxy) propane 6, 6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / resorcinol 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine / 2-methylresorcinol 6,6a, 7,8,9,10- Hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / 2-amino-3-hydroxypyridine

- 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / 3-amino-2-methylamino-6-methoxypyridine

6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazin-3-amine / 1-naphthol 6,6a, 7,8,9,10- Hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / 1,5-dihydroxynaphthalene

- 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c] - [1,4] benzoxazin-3-amine / 2,7-dihydroxynaphthalene

1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 5-amino-2-methylphenol

1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 3-amino-2-chloro-6-methylphenol

1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 2,4-dichloro-3-aminophenol

- 1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 2- (2,4-diaminophenoxy) ethanol

- 1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 1,3-bis (2,4-diaminophenoxy) propane

1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazin-8-amine / resorcinol 1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 2-methylresorcinol 1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino- [3, 4-c] [1, 4] benzoxazine-8-amine / 2-amino-3-hydroxypyridine 1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1 , 4] benzoxazin-8-amine / 3-amino-2-methylamino-6-methoxypyridine

1, 2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 1-naphthol 1, 2,4a, 5-tetrahydro 4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 1,5-dihydroxynaphthalene. 1,2,4a, 5-tetrahydro-4H- [1,4] oxazino [3,4-c] [1,4] benzoxazine-8-amine / 2,7-dihydroxynaphthalene The hair colorants according to the invention contain both the developer components and the coupler components preferably in an amount of 0.005 to 20% by weight, preferably 0 , 1 to 5% by weight, in each case based on the total 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 proved to be useful, 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, may be included. In a further embodiment of the present invention, the colorants may contain at least one precursor of a naturally-analogous dye.

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. 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.

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.

Highlights within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-

Propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular the 5,6-dihydroxyindole.

The indoline or the indole derivatives can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.

The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment, it may be preferred according to the invention, the indoline or

Indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-

Amino acids are arginine, ornithine, lysine, serine and histidine, especially arginine.

In addition to the p-phenylenediamine derivatives of the formula (I) according to the invention, the colorants according to the invention can be used in a further preferred embodiment of the present invention

For shading contain one or more substantive dyes. 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.

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

Preferred anionic substantive dyes are those under international names or

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.

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) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as described for example in EP-A2-998 908, to the is explicitly referred to at this point, are called in the claims 6 to 1 1.

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

CH ₃ SO ₄ ^"

Cl ^"

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. 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 HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 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-hydroxyethyl) amino-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 e 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, minor amounts of other components may be included, as far as these do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

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. Furthermore, natural dyes can also be used as substantive dyes. As natural dyes in the context of the invention are dyes to be understood, which are obtained from parts of plants. For this purpose, preferably different parts of plants, depending on the desired dye. It is understood, however, that a dye can be obtained from more than one plant part. The preferred plant parts for obtaining natural dyes are included in the group formed by root, stems, bark, heartwood, resin, flower, leaf, fruit and sap. For the purposes of the invention it is furthermore not necessary for natural dyes that the agents obtained from the plant parts represent dyes as such, but that they optionally also represent dye precursors which form the actual dye by subsequent chemical reactions. Mentioned here in particular the oxidation with atmospheric oxygen to form the chromophore.

It is not necessary, in particular for the purposes of the invention, that the dyes or dye precursors in each case represent uniform compounds. Due to different, non-uniform extraction methods such as different extraction or fermentation conditions or by using different, regional subspecies and different parts of plants or partly from culture-historical tradition, some natural dyes mentioned deliberately contain no uniform compounds, but mixtures of dyes, dye precursors and other components , in particular tannins.

For the purposes of the invention, a natural dye is, of course, also understood to mean a discrete colorant compound isolated from such a mixture or optionally also a plurality of discrete colorant compounds isolated from such a mixture. Detailed descriptions of the natural dyes can be found inter alia in the handbook of natural dyes known to those skilled in the art: occurrence, use, detection, H. Schweppe, ecomed Verlagsgesellschaft, 1993, Landsberg / Lech.

In particular, the cosmetic compositions according to the invention comprise at least one natural dye selected from the group comprising diaryloylmethane dyes, naphthoquinone dyes, flavonoid dyes, anthraquinone dyes, betalain dyes, gallotannin dyes and indigoid dyes. With regard to the definitions of these classes of dyes, reference should be made explicitly to the corresponding passages of the priority document at this point.

Particularly preferred natural dyes according to the present invention are those obtained from a plant selected from the group consisting of Indigofera tinctoria, Curcuma longa, Lawsonia inermis, Chamomilla recutita, Quercus robur, Rosmarinus officinalis, Rheum undulatum and Beta vulgaris.

Very particular preference is given to the group which is formed from diaryloylmethane dyes, naphthoquinone dyes and indigoid dyes.

Very particular preference is given in the cosmetic compositions according to the invention to natural dyes of plants selected from the group consisting of Curcuma longa (turmeric, CI Natural Yellow 3), Lawsonia inermis (Henna, red, CI Natural Orange 6) and Indigofera tinctoria (Henna, black, Cl. Natural Blue 1). The natural dyes are each preferably used in an amount of 0.001 to 20 wt .-%, based on the total application preparation. The total amount of natural dyes is preferably at most 20% by weight.

The colorants of the invention may further contain all known for such preparations active ingredients, additives and excipients. In many cases, the colorants 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, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.

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

Nonionic surfactants contain as hydrophilic group z. Example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and Polyglykolethergruppe. Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

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

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds. Particular preference is given to those alkylpolyglycosides in which R ¹ consists essentially of C ₈ and C ₁₀ -alkyl groups, essentially of C ₁₂ and C ₁₄ -alkyl groups, essentially of C ₈ - to C ₁₆ -alkyl groups or essentially of C ₁₂ - to C ₁₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, Allose, Altrose, Mannose, Gulose, Idose, Talose and Sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred. The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

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

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ ⁽⁾ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyldimetic acid thylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, acylaminoethylaminopropionat the coconut and the Ci _Σ -is-acyl sarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkyl methylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

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

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

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

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium 80th).

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

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred. Furthermore, the colorants of the invention may contain other active ingredients, auxiliaries and additives, such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, 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 acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate ^ -hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic 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. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as

Amylose, amylopectin and dextrins, clays such as Bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, such as soybean 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,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and

Diethylene glycol, fiber structure-improving agents, in particular mono-, di- and oligosaccharides such as 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 conventional acids, in particular

Pleasure acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops,

Chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle,

Horse-chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi, melon,

Orange, Grapefruit, Sage, Rosemary, Birch, Mallow, Meadowfoam, Quendel, Yarrow,

Thyme, balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.

Cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

fatty acid,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids, Swelling and penetration 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,

Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants

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 cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

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

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 of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.

The actual oxidative coloring of the fibers can be done basically with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate. However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can be in a range between 15 and 40 ⁰ 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 omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used. A second object of the present invention is a process for coloring keratinic fibers, in which a hair colorant according to the invention is applied to the fibers and after a

Reaction time is rinsed off again.

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.

A third object of the present invention is the use of a p-phenylenediamine derivative of the formula (I)

wherein the radicals R1 and R2 are independently a hydrogen atom, a hydroxy group, a Ci-Cβ-alkoxy group, a halogen atom, a d-Cβ-alkyl group, a C ₂ -C ₆ - alkenyl group, a Ci-Cβ-monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, an aryl group, a heteroaryl group or an amino group, the radical A is a group -CR 2 H-, an oxygen atom or a group NR 3, wherein R 3 is a hydrogen atom, a Ci-Cβ-alkyl group, a C ₁ -C ₆ -monohydroxyalkyl group or a C ₂ -C ₆ -polyhydroxyalkyl group, and - n is either the number 1, 2 or 3 as a developer component for the oxidative coloring of keratinic fibers.

A fourth subject of the present invention relates to a series of compounds of formula (I) itself. These are the compounds of the formula (Ia)

in which

- The radicals R1 and R2 independently of one another represent a hydrogen atom, a

Hydroxy group, a Ci-C ₆ alkoxy group, a halogen atom, a Ci-C ₆ alkyl group, a C ₂ -C ₆ - Alkenyl group, a Ci-C ₆ monohydroxyalkyl, a C ₂ -C ₆ -polyhydroxyalkyl group, an aryl group, a heteroaryl group or an amino group, and - n represents either the number 1, 2 or 3, with the proviso that at least one of Radicals R1 and / or R2 is different from hydrogen. With regard to further preferred embodiments of the use according to the invention and of the novel compounds of the formula (Ia), mutis mutandis applies to what has been said about the agents according to the invention. The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way.

Exemplary embodiments 1 Syntheses

1.1 Synthesis of 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c1- [1,1'-benzoxazine-7-amine hydrochloride

(x 2 HCl) 1.1.1 Synthesis of 2,3,3a, 4-tetrahydro-7-nitro-1H-pyrrolo [2,1-c] [1,4] benzoxazine

To a solution of 7.6 g (0.075 mol) of pyrrolidine methanol (L-prolinol) in 100 ml of dry

Dimethylsulfoxide was added to 10.5 g (0.159 mol) of potassium hydroxide (85%). Subsequently were

10.0 g (0.063 mol) of 3,4-difluoronitrobenzene added dropwise within 5 minutes. Then that became

Reaction mixture for 4 hours at 60 ⁰ C stirred. After cooling, the batch was adjusted to 500 ml

Ice water poured. This precipitated a brown solid, which was filtered off, washed with water and dried in vacuo.

Yield: 11.0g (79%)

¹ H-NMR (400 MHz, DMSOd ₆ ): δ [ppm] = 1.40-1.50 (m, 1H); 1.90-2.00 (m, 1H); 2.05-2.15 (m, 2H); 3,25-

3.45 (m, 2H); 3.55-3.65 (m, 2H); 4.60 (dd, 1H); 6.60 (d, 1H); 7.55 (d,

1H); 7.79 (dd, 1H) 1 ³ C-NMR (400 MHz, DMSOd ₆ ): δ [ppm] = 22.9; 27.8; 47.0; 55.5; 67.7; 109.4; 110.0; 119.9; 135.0;

140.7; 141.0

1.1.2 Synthesis of 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c] [1,4] benzoxazine-7-amine hydrochloride (x 2 HCl)

There were 9.9 g (0.045 mol) of 2,3,3a, 4-tetrahydro-7-nitro-1H-pyrrolo [2,1-c] [1,4] -benzoxazine in a mixture of 1400 ml of ethanol and 40 ml of water dissolved. After addition of 1.2 g of the hydrogenation catalyst (Pd / C, 5%), the nitro group was reduced in an autoclave at room temperature and a hydrogen pressure of 10 bar. After the addition of 50 ml (0.014 mol) of dilute hydrochloric acid was separated from the catalyst and the filtrate was completely evaporated to dryness, resulting in light brown, slightly hygroscopic crystals. Yield: 10.8 g (91%)

¹ H-NMR (400 MHz, DMSO-d ₆ / D ₂ O): δ [ppm] = 1.41-1.56 (m, 1H); 1.87-2.19 (m, 3H); 3.15-3.22 (m, 1H);

3.41-3.48 (m, 1H); 3.50-3.60 (m, 2H); 4.52 (dd, 1H); 6.79 (d, 1H);

6.91 (m, 2H)

13 C-NMR (400 MHz, DMSOd ₆ / D ₂ O): δ [ppm] = 25.0; 29.4; 51.1; 57.2; 69.4; 112.6; 116.1; 118.2; 122.2;

135.3; 145.5

1.2 Synthesis of 2.2. e.ay.δ.g.iO-hexahydrodopyrido ^ .i-ci-fiibenzoxazine-S-amine hydrochloride (x

1.5 HCl) 1.2.1 Synthesis of 6,6a, 7,8,9,10-hexahydro-3-nitropyrido [2,1-c] [1,4] benzoxazine

To a solution of 8.6 g (0.075 mol) of 2-piperidinemethanol in 100 ml of dry dimethylsulfoxide

Add 10.5 g (0.159 mol) of potassium hydroxide (85%). Subsequently, 10.0 g (0.063 mol) of 3,4-

Difluornitrobenzen added dropwise within 10 minutes. Then the reaction mixture was for 4

Hours at 60 ⁰ C stirred. After cooling, the batch was poured onto 500 ml of ice water.

This precipitated a brown solid, which was filtered off, washed with water and dried in vacuo.

Yield: 11.8 g (80%)

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 1.13-1.26 (m, 1H); 1.39-1.56 (m, 2H); 1.68-1.88 (m, 3H); 2,73-

2.82 (m, 1H); 3.20-3.28 (m, 1H); 3.90-3.95 (m, 1H); 4.01-4.07 (m, 1H);

4.25-4.30 (dd, 1H); 6.99 (d, 1H); 7.46 (d, 1H); 7.72 (dd, 1H)

13 C-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 21.1; 24.3; 26.5; 45.8; 52.2; 68.5; 110.9; 111.2; 118.6; 136.7;

142.4; 143.0

1.2.2 Synthesis of 2.2.6.6a, 7,8,9,10-hexahydro-pyrido [2,1-c] [1,4] benzoxazine-3-amine hydrochloride (x1.5 HCl)

There were 10.5 g (0.045 mol) of 6,6a, 7,8,9,10-hexahydro-3-nitropyrido [2,1-c] [1,4] benzoxazine in a mixture of 1700 ml of ethanol and 100 ml Water dissolved. After addition of 1.0 g of the Hydrogenation catalyst (Pd / C, 5%) was the nitro group in an autoclave at room temperature and a

Reduced hydrogen pressure of 10 bar. After the addition of 50 ml (0.143 mol) of dilute hydrochloric acid was separated from the catalyst and the filtrate was completely evaporated to dryness, resulting in light gray hygroscopic crystals.

Yield: 11.4 g (98%)

¹ H-NMR (400 MHz, DMSOd ₆ ): δ [ppm] = 1, 14-1, 26 (m, 1H); 1, 37-1, 60 (m, 2H); 1, 68-1, 81 (m, 3H); 2,51-

2.61 (m, 1H); 2.97-3.06 (m, 1H); 3.81-3.88 (m, 1H); 3.93-3.99 (m, 1H);

4.24 (dd, 1H); 6.80 (d, 1H); 6.87 (dd, 1H); 7.02 (d, 1H) 1 ³ C-NMR (400 MHz, DMSOd ₆ ): δ [ppm] = 22.1; 24.0; 25.9; 45.6; 52.8; 68.9; 111, 0; 114.8; 1 15.8; 123.1;

134.2; 145.1

2 colorations

2.1 Experimental procedure

The cream base used had the following composition: Hydrenol D ^{® 1} 8.5 wt .-%

Lorol® ^® tech. ² 2.0% by weight

Texapon ^® NSO ³ 20.0 wt .-%

Dehyton ^® K ⁴ 12.5 wt .-%

Eumulgin B2 ^{® 5} 0.75 wt .-%

Propylene glycol 5.0% by weight

Sodium sulfite 1, 0% by weight

Ammonium sulfate 1, 0 wt .-%

Developer component 3mmol

Coupler component 3mmol

Water ad 100

¹ C ₁₆ . ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² C "i ₂ - ₁₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis)

³ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

⁴ N, N-dimethyl-N, Cs-iβ-cocoamidopropyl ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

Hydrenol D and Lorol techn. were melted together with Texapon NSO-UP, Dehyton K and Eumulgin B2 at 80 ⁰ C. Then, the melt was emulsified with the sodium sulfite dissolved in a part of the water and ammonium sulfate. The developer according to the invention was dissolved in propylene glycol and a further portion of the stated amount of water with heating and added with stirring. The coupler was also dissolved in a portion of the indicated amount of water and added with stirring. Then the formulation was made up to 100% with water and stirred cold. The coloring cream thus obtained was mixed in a ratio of 2: 1 with the following developer dispersion having a hydrogen peroxide content of 3%. Dipicolinic acid 0.1% by weight

Sodium pyrophosphate 0.03% by weight

Turpinal SL ^{® 6} 1, 50 wt .-%

Texapon ^® N28 ⁷ 2.00 wt .-%

Acrysol ^® 22 ⁸ 0.60 wt .-%

Hydrogen peroxide, 50% 6.00% by weight

Sodium hydroxide, 45% 0.80% by weight

Water ad 100% by weight

⁶ 1-Hydroxyethane-1, 1-diphosphonic acid (about 58 - 61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

⁷ lauryl ether sulfate sodium salt (at least 26.5% active ingredient content, INCI name: Sodium Laureth Sulfate) (Cognis)

⁸ acrylic polymer (about 29.5 - 30.5% solids in water, INCI name: Acrylates / Steareth-20 Methacrylate Copolyme)

For the dyeing process, four times the amount of ready-to-use mixture was applied to one strand of 80% gray hair (Kerling). After a contact time of 30 minutes at 32 ⁰ C, the locks were rinsed and washed out with a conventional shampoo. The streaking of the streaks was visually assessed under the daylight lamp after drying. The staining results are summarized in the table below.

2.2 Coloring with 2,3,3a, 4-tetrahydro-1H-pyrrolo [2,1-c1- [1,1'-benzoxazine-7-amine hydrochloride (x 2 HCl) as developer component

Coupler component obtained shade / color intensity

Resorcinol gray / ++

3-Amino-2-methylamino-6-methoxypyridine violet-gray / +++

5-amino-2-methylphenol blue-gray / +++

3-amino-2-hydroxypyridine dark purple / +++

1, 3-bis (2,4-diaminophenoxy) propane dark blue / +++

2,7-Dihydroxynaphthalene gray / ++

The color intensities were evaluated as follows:

+++ high intensity ++ medium intensity + low intensity 2.3 Coloring with 6,6a, 7,8,9,10-hexahydro-pyrido [2,1-c1- [1,4-benzoxazin-3-amine hydrochloride (x 1, 5 HCl) as a developer component

Coupler component obtained shade / color intensity

Resorcinol olive gray / ++

3-amino-2-methylamino-6-methoxypyridine dark green / +++

5-amino-2-methylphenol brown-gray / ++

3-amino-2-hydroxypyridine gray-brown / +++

1, 3-bis (2,4-diaminophenoxy) propane dark blue / +++

2,7-Dihydroxynaphthalene blue-gray / ++

The color intensities were evaluated as follows:

+++ high intensity ++ medium intensity + low intensity

Claims

Patent claims

1. agent for coloring keratinic fibers, in particular human hair, characterized in that it comprises in a cosmetically acceptable carrier as the developer component at least one p-phenylenediamine derivative of the formula (I)

contains, where

- the radicals R1 and R2 are independently a hydrogen atom, a hydroxy group, a C _r C ₆ alkoxy group, a halogen atom, a Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a -C ₆ monohydroxyalkyl, a C ₂ -C ₆ polyhydroxyalkyl group, an aryl group, a heteroaryl group or an amino group,

- the group A represents a group -CR2H-, an oxygen atom or a group NR3, wherein R3 stands for a hydrogen atom, a Ci-C ₆ alkyl group, a C ₁ -C ₆ - monohydroxyalkyl or C ₂ -C ₆ - Polyhydroxyalkyl group, and n is either the number 1, 2 or 3.

2. Composition according to claim 1, characterized in that R ₁ is hydrogen, a C ₁ -C ₆ - alkoxy group, a halogen atom, a C-ι-C ₆ alkyl group or a C ₁ -C ₆ - Monohydroxyalkylgruppe.

3. Composition according to one of claims 1 or 2, characterized in that R1 represents a hydrogen atom, a methyl group or a chlorine atom.

4. Composition according to claim 3, characterized in that R1 represents a hydrogen atom.

5. Composition according to one of claims 1 to 4, characterized in that R2 represents a hydrogen atom, a C-ι-C ₆ alkyl group, a hydroxy group or a C ₁ -C ₆ - Monohyd roxya Iky Ig ru ppe.

6. Composition according to one of claims 1 to 5, characterized in that the radical R2 is a hydrogen atom, a hydroxy group, a methyl group or a hydroxymethyl group.

7. Composition according to one of claims 1 to 6, characterized in that A represents a group -CR2H- or an oxygen atom.

8. Composition according to one of claims 1 to 7, characterized in that n stands for 1.

9. Composition according to one of claims 1 to 8, characterized in that n stands for 2.

10. Composition according to one of claims 1 to 9, characterized in that it contains at least one coupler component.

11. A method for coloring keratinous fibers, wherein an agent according to any one of claims 1 to 10 is applied to the fibers and rinsed again after a contact time.

12. Use of a p-phenylenediamine derivative of the formula (I)

in which

- the radicals R1 and R2 are independently a hydrogen atom, a hydroxy group, a C _r C ₆ alkoxy group, a halogen atom, a Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a -C ₆ monohydroxyalkyl, a C ₂ -C ₆ polyhydroxyalkyl group, an aryl group, a heteroaryl group or an amino group,

- the group A represents a group -CR2H-, an oxygen atom or a group NR3, wherein R3 stands for a hydrogen atom, a C-rC ₆ alkyl group, a C ₁ -C ₆ - monohydroxyalkyl or C ₂ -C ₆ - Polyhydroxyalkylgruppe, and n is either the number 1, 2 or 3 as a developer component for the oxidative coloring keratinischer fibers.

13. Compounds of the formula (Ia)

where the radicals R1 and R2 are independently a hydrogen atom, a C ₁ - C ₆ alkoxy group, a halogen atom, a _C-ι-C6 alkyl group, a C ₂ -C ₆ alkenyl group, a C-ι-C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, an aryl group, a heteroaryl group or an amino group, and n is either the number 1, 2 or 3, with the proviso that at least one of R 1 and / or R _{2 is} from Hydrogen is different.