WO2010046190A2

WO2010046190A2 - Tricyclic aldehydes and c,h acidic compounds

Info

Publication number: WO2010046190A2
Application number: PCT/EP2009/062216
Authority: WO
Inventors: Wibke Gross; Doris Oberkobusch; Ralph Nemitz
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2008-10-21
Filing date: 2009-09-21
Publication date: 2010-04-29
Also published as: DE102008052618A1; WO2010046190A3

Abstract

The invention relates to an agent for coloring fibers containing keratin, particularly human hair, containing at least one compound of formula (I) in combination with C,H acidic compounds, to the use of said combination in agents for coloring fibers containing keratin, for color refreshing or shading of fibers containing keratin that have already been colored, and to a method for coloring fibers containing keratin, particularly human hair.

Description

"Tricyclic aldehydes and C, H-acidic compounds"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains specific tricyclic aldehydes in combination with C, H-acidic compounds, the use of this combination in agents for dyeing keratin fibers, for color refreshing or nuancing already dyed keratin-containing fibers and a method for dyeing keratin-containing fibers, in particular human hair.

In order to provide color-modifying cosmetic agents, in particular for the skin or keratin-containing fibers such as human hair, the skilled person knows various systems depending on the requirements of the coloration or color change.

If, in general, substrates are to be lightened or even bleached, the substrate-coloring synthetic and / or natural dyes are usually decolorized by oxidation using appropriate oxidizing agents, such as hydrogen peroxide. For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings, however, usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading. For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable change in shade or even a visible, homogeneous color loss occurs much more quickly.

Another possibility for Farbve ränderung provides 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 C, H-acidic compounds and compounds having primary or secondary amino groups or hydroxy groups, which are in turn 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 suitable alone for dyeing keratinhaltiger fibers alone. In combination they form in a non-oxidative process the so-called called oxo dyeing dyes. 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 method of oxo staining can be readily combined with the oxidative staining system.

The range of commercially available hair colors contains not only the luminous fashion tones but also a large variety of natural tones, which in particular encompass a wide range of brown shades. Especially for covering the gray hair and restoring the original hair color, these natural tones are important. When using the oxo dyeing system, the production of a brown shade is usually achieved by mixing different bright shades. It is necessary to use yellow component dyes, red component dyes and blue component dyes together. Due to this mixing process, the availability of a large number of dye components is essential to make the full range of desired nuances accessible.

In particular, for the formulation of natural-looking hair shades, it is of great importance to be able to produce the complete color spectrum with a dyeing system. In addition to the formation of red and brown shades for natural tones and fashionable copper nuances, blue shades are also of great importance for the formulation of dark browns and blacks. The requirement profile for the nuances produced in this way not only encompasses a comprehensive color palette, but also a good leveling ability, in order to avoid different absorption on differently damaged parts of the hair and a resulting inconsistent color result. Also, a nuance due to different levels of wash or light fastness of the different dyes used over time may be subject to color shifts that are not desired by the consumer and therefore necessarily be avoided in the development of new dye combinations for Oxofärbesysteme.

Hair dyeing systems which claim the use of a combination of carbonyl compounds, in particular aldehydes, and C, H-acidic compounds are already known to the person skilled in the art from the patent literature. The documents EP1534227, EP1778176, EP1789014, WO2006 / 119819, WO2007 / 079802 and WO2008 / 074578 mention dyeing systems which describe dyeings with C, H-acidic compounds. In many cases, the carbonyl compounds are aldehydes structurally derived from hydroxy-substituted benzene and naphthaldehyde derivatives, respectively. However, the blue shades known to the person skilled in the art hitherto known from the state of the art and capable of being produced by means of a staining system from suitable aldehydes and C, H-acidic compounds have massive weaknesses with regard to the application-specific requirement profile. In particular, the washing fastness and the leveling ability of the blue shades produced by means of literature-known formulations are still in need of considerable improvement.

It is therefore an object of the present invention, within the framework of a new dyeing system for keratin-containing fibers, in particular human hairs, which does not use oxidizing agents, to provide novel aldehydes with which very stable blues can be produced in combination with the suitable C, H-acidic compounds even after repeated shampooing of the hair no color weakening or color shift. The color shades should be at least equivalent in terms of color depth and fastness properties, such as light, rubbing and washing fastness and welding and cold wave fastness, the usual oxidation hair dyes, but without necessarily on oxidizing agents such. B. H ₂ O ₂ instructed to be. In particular, it is the object of the present invention to provide corresponding blue shades with a high stability against acidic washing and shampoo solutions, as they have not yet been described in the literature.

It has been found that special tricyclic aldehydes in combination with C, H-acidic compounds are outstandingly suitable for dyeing keratin-containing fibers, even in the absence of oxidizing agents. They give colorations with excellent brilliance and color depth and achieve especially blue shades. In particular, colorations having improved fastness properties are obtained.

A first subject of the invention is therefore a means for changing the color of keratinous fibers, which is characterized in that it is obtained by mixing at least two components, wherein the first component (component A) at least one compound according to formula (I) and / or a their physiologically acceptable salts

(I) contains, in which

R1 roup is a hydrogen atom, a Ci-C ₆ alkyl group, a C ₂ -C ₆ -alkyl keny Ig, a Ci-C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Hydroxyg roup, a d- C ₆ -alkoxy group, a C 1 -C ₆ -alkoxy-C 1 -C ₄ -alkyl group, a halogen atom, a carboxy group, a sulfonic acid group, a C 1 -C ₆ -alkoxycarbonyl group, a nitrile group, a nitro group, an amino group, a mono (C ₁ -C ₆ alkyl) amino group, a di (C ₁ -C ₆ alkyl) amino group, an optionally substituted aryl group or an optionally substituted heteroaryl group, and n is a natural number of 2 to 5, and the second component (component B) contains at least one C, H-acidic compound.

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.

In a preferred embodiment, agents according to the invention are characterized in that component A contains at least one compound according to formula (I) and / or one of its physiologically tolerable salts, in which R 1 is a hydrogen atom, a C 1 -C 6 -alkyl group, a hydroxy group, a C 1 -C 4 -alkyl group -C ₆ alkoxy group or a halogen atom.

Particularly good effects were found with compounds of the formula (I), in whose structure n stands for one of the numbers 2 or 3.

It is particularly preferred if at least one of the following compounds of the formula (I) is present in the composition according to the invention:

It is particularly preferred if the radicals R 1 is a hydrogen atom and n is one of the numbers 2 or 3.

Particularly preferred compounds according to formula (I) are 2,3,6,7-tetrahydro-5H- [1,4] oxazino [2,3,4-ij] quinoline-9-carbaldehyde and / or one of its physiologically tolerable salts.

Further suitable components A according to the invention are those derivatives of the compounds of the formula (I) in which the reactive carbonyl group is derivatized such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the C, H-acids Compounds of component B is always present. These derivatives are preferably addition compounds a) of amines and derivatives thereof to form imines or oximes as addition compound b) of alcohols to form acetals as addition compound c) of water to form hydrates as addition compound to the carbon atom of the carbonyl group in compounds of formula ( I).

C, H-acidic compounds are generally considered to be those compounds which carry a hydrogen atom attached to an aliphatic carbon atom, activation of the corresponding carbon-hydrogen bond being brought about as a result of electron-withdrawing substituents. In principle, there are no limits to the choice of C, H-acidic compounds, as long as, after the Knoevenagel condensation with the tricyclic aldehydes of the formula (I) according to the invention, a compound visibly colored to the human eye is obtained.

According to the invention, these are preferably those C, H-acidic compounds which contain an aromatic and / or a heterocyclic radical. The heterocyclic radical may again be aliphatic or aromatic.

Agents preferred according to the invention are characterized in that they are obtained by mixing a component A containing at least one compound according to formula (I) and a component B, wherein component B contains as C, H-acidic compound at least one compound selected from the group which is formed from compounds according to formula (II),

^R5 vV ^R2

R4 ^ R3

^X (II), in which

R _{2 is} a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aryl-Ci-Cβ-alkyl group or an optionally substituted heteroaryl-Ci-Cβ-alkyl group,

R3 and R4 each independently represent a hydrogen atom, a C-rC alkyl group, or _C6 alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, an optionally substituted aryl Ci-C ₆ an optionally substituted heteroaryl-Ci-C ₆ -alkyl group, with the proviso that at least one of the substituents R3 and R4 is not hydrogen, and that the substituent on the carbon atom, which with the heterocycle of formula (II) is linked, at least two

Carries hydrogen atoms, R 5 is a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C C ₂ -C ₆ -alkyl group, an optionally substituted aryl-d-Cβ-alkyl group or an optionally substituted heteroaryl-C ₁ -C ₆ -alkyl group, Y represents an oxygen atom, a sulfur atom or a group NR ', wherein R' represents a hydrogen atom , an aryl group, a heteroaryl group, a Ci-Cβ-alkyl group or a C-rC ₆ arylalkyl group, and X ^'is a physiologically acceptable anion, from compounds of the formula (IM)

^ U - ^CN HeI ^ CH ₂

(III), in which

Het is an optionally substituted heteroaromatic and

L is a direct bond or a carbonyl group, and / or their physiologically acceptable salts.

In this case, particularly intense and colorfast blue shades are obtained when the C, H-acidic compounds of component B from at least one compound of the above formula (II) is selected. Equivalent to the compounds of the formula (II) are their enamine forms. Reference is hereby made expressly to the document W0-A1-2004 / 022016, to the full contents of which reference is made.

At least one group R3 or R4 according to formula (II) is necessarily a C ₁ -C ₆ -alkyl group or an appropriately substituted alkyl chain. This alkyl group carries at the α- carbon atom, ie the carbon which is linked to the heterocycle of the formula (II), at least two hydrogen atoms.

Preferably, the compounds according to formula (II) 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- oxopyrimidinium, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium, 1, 2 Dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxopyrimidinium, 1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxopyrimidinium, 1,2 Dihydro-1, 3,4-trimethyl-2-oxopyrimidinium, 1, 2-dihydro-1,3-di-ethyl-4-methyl-2-oxopyrimidinium, 1,2-dihydro-1,3-dipropyl-4 -methyl-2-oxopyrimidiniums, 1, 2-dihydro-1, 3-di (2-hydroxyethyl) -4-methyl-2-oxopyrimidiniums, 1, 2-dihydro-1, 3-diphenyl-4-methyl- 2-oxopyrimidinium, 1-A-1-yl-1, 2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl- 2-oxopyrimidiniums, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxopyrimi- diniums, 1, 2-dihydr o-1,3-diethyl-4,6-dimethyl-2-thioxopyrimidinium, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium, 1,2-dihydro-1,3-diene di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyridine midiniums, 1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxopyrimidiniums, 1, 2-dihydro-1, 3,4-trimethyl-2-thioxopyrimidiniums, 1, 2-dihydro- 1,3-diethyl-4-methyl-2-thioxopyrimidiniums, 1, 2-dihydro-1, 3-dipropyl-4-methyl-2-thioxopyrimidiniums, 1, 2-dihydro-1, 3-di (2- Hydroxyethyl) -4-methyl-2-thioxopyrimidiniums, 1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxopyrimidiniums, 1, 2-dihydro-3,4-dimethyl-2-oxoquinazolinium and 1 , 2-dihydro-3,4-dimethyl-2-thioxochinazoliniums.

X ^" in formula (II) and in the above lists is preferably halide, benzenesulfonate, p-toluenesulfonate, C 1 -C ₄ -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate Anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate used as X ^' .

Preferably, the compounds according to formula (III) are selected from 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-trimethylpyrrole-3-oyl) acetonitrile, 1 / - / - benzimidazol-2-ylacetonitrile, 1 / - / - benzothiazole -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-benzoquinoline-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 f butyl ester, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) acetonitrile and 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazole-3- oyl) acetonitrile. Particularly preferred is 1 / - / - benzimidazol-2-ylacetonitrile.

Very particularly preferred agents according to the invention are characterized in that they contain as C, H-acidic compound of component B at least one compound which is selected from the group formed from salts of 1, 2-dihydro-1, 3,4,6 Tetramethyl-2-oxopyri- midiniums, salts of 1, 2-dihydro-1, 3,4-trimethyl-2-oxopyrimidiniums, salts of 1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxopyrimidiniums , Salts of 1-A.llyl-1, 2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums, salts of 1, 2-dihydro-1- (2-hydroxyethyl) -3,4,6 trimethyl-2-oxopyrimidiniums and 2- (cyanomethyl) benzimidazole.

In a further embodiment, it may be advantageous for expanding the color spectrum to add at least one further component C to the compositions according to the invention in addition to at least one compound of formula (I) in component A and at least one C, H-acidic compound in component B. Component C contains at least one reactive carbonyl compound which is different from compounds of formula (I) and serves to nuance the base clay. The reactive carbonyl compounds in component C according to the invention have at least one carbonyl group as a reactive group which reacts with the C, H-acidic compound of component B to form a carbon-carbon bond. Preferred reactive carbonyl compounds are aldehydes and ketones, especially aromatic aldehydes. Furthermore, according to the invention, those compounds in component C can also be used 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 C, H-acidic compounds of component B is always present. These derivatives are preferably addition compounds a) of amines and their derivatives to form imines or oximes as the addition compound b) of alcohols to form acetals or ketals as the addition compound c) of water to form hydrates as the addition compound to the carbon atom of the carbonyl group of the reactive carbonyl compound ,

Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular with one or more hydroxyl, alkoxy or amino substituents, are preferably used in the agents according to the invention as the reactive carbonyl compound in component C.

The derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component C are particularly preferably selected from certain aldehydes. Here, preferred are agents according to the invention which additionally contain in component C at least one reactive carbonyl compound which is selected from the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, A-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, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, A-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy -2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methyl-benzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydrox y-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxybenzaldehyde 4-ethoxy-2-hydroxy-benzaldehyde 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-trimethoxbenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2- Hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxy- benzaldehyde, 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-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde 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, A-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, A-hydroxy-3, 5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-Br om-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-naphthalde-hyd, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy- 1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl- 3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2- nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2- Hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-di-n itrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4- Dimethylamino-2-methylbenzaldehyde, 4-diethylaminocinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal. These representatives are also the most preferred additional reactive carbonyl compounds of component C.

In a third embodiment, the colorant additionally contains at least one reaction product (hereinafter referred to as reaction product RP) of a compound of formula I and a compound of component B as direct dye. Such reaction products RP can z. Example, be obtained by heating the two reactants in an aqueous neutral to slightly alkaline medium, wherein the reaction products RP precipitate either as a solid from the solution or isolated by evaporation of the solution thereof.

For the synthesis of the reaction products RP, molar ratios of component B to the compound according to formula I of about 1: 1 to about 1: 2 may be useful. The above-mentioned compounds of the formula (I), the C, H-acidic compounds of the component B and optionally the reactive carbonyl compounds of the component C are each preferably in an amount of 0.03 to 65 mmol, especially from 1 to 40 mmol, based on 100 g of the total colorant used. Corresponding agents according to the invention in which the compounds of the formula (I), the C, H-acidic compounds of component B and, if appropriate, the reactive carbonyl compounds of component C are each in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, are preferred.

It may be preferred according to the invention if the agent contains at least one further coloring component which is selected from (a) oxidation dye precursors and / or (b) nature-analogous dyes and / or (c) substantive dyes.

As oxidation dye precursors, the compositions according to the invention may contain at least one developer component and optionally at least one coupler component.

Preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1, 2-dihydroxyethyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole-1 -yl) - propyl] amine, N, N'-bis (2-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- (1,2-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4- Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triamino-pyrimidine, and the physiologically acceptable salts of these Verbindu nts. Very particularly preferred developer components are p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- ( 1 H-imidazol-1-yl) propyl] amine, and / or 4,5-diamino-1- (2-hydroxyethyl) pyrazole and their physiologically acceptable salts. The developer components are preferably used in an amount of 0.0001 to 0.5 wt .-%, preferably 0.001 to 0.2 wt .-%, each based on the ready-to-use agent.

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 developer component is additionally used when using at least one coupler 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. According to the invention, preferred coupler components are selected from 3-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, 2-aminophenol, 3-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-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-dimethoxy-pyridine, 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, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or their physiologically acceptable salts. Particularly preferred are resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1 Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 2-amino-3-hydroxypyridine and 1-naphthol and their physiologically acceptable salts. The coupler components are preferably used in an amount of 0.0001 to 0.5 wt .-%, preferably 0.001 to 0.2 wt .-%, each based on the ready-to-use agent.

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. 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.

The dye precursors of naturally-analogous dyes are each preferably used in an amount of from 0.001 to 5% by weight, based on the total application preparation. The total amount of substantive dyes is preferably at most 3% by weight.

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, especially 5,6-dihydroxyindoline. 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, especially 5,6-dihydroxyindole. 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 nitro phenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, in particular from 0.05 to 5 wt .-%, each 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.

Particularly suitable anionic direct dyes are FD & C Yellow No. 6, Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 23, Acid Yellow 36, Acid Yellow 73, Acid Orange 3, Acid Orange 6, Acid Orange 7, Acid Orange 24, Acid Red 4), Acid Red 14 Acid red 18, acid red 27, acid red 33, acid red 35, acid red 51, acid red 52, acid red 73, acid red 87, acid red 92, acid red 95, acid red 184, acid red 195, pigment Red 57: 1, FD & C Red No. 4 Acid Green 25, Acid Green 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Blue 25, Acid Blue 62, Acid Blue 74, Acid Violet 9, Acid Violet 43, Acid Brown 13, Acid Blue. Acid Black 1, Acid Black 52, Food Black no. 1, 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (bromophenol blue), 3,3 ', 3 ", 4,5,5', 5", 6-octabromophenolsulfonephthalein (tetrabromophenol blue).

Preferred cationic substantive dyes are cationic triphenylmethane dyes, such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems which are substituted by a quaternary nitrogen group, for example Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as described for example in EP-A2-998 908, which is incorporated herein by reference the claims 6 to 1 1 called. The compounds also known as Basic Yellow 87, Basic Orange 31 and Basic Red 51 are most preferred cationic substantive dyes. 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 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 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-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 and 2-chloro-6-ethylamino-4-nitrophenol.

It is not necessary that the optionally contained 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. Furthermore, naturally occurring dyes can also be used as substantive dyes, such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, walnut, buckthorn bark, sage, bluewood, madder root, catechu and alkano root are.

To obtain further and more intense colorations, the compositions according to the invention may additionally contain color enhancers. The color intensifiers are preferably selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methyl- imidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine, any mixtures thereof, derivatives and their physiologically acceptable salts. The color intensifiers mentioned above can be used in an amount of 0.03 to 10% by weight, in particular 0.5 to 5% by weight, in each case based on 100 g of the ready-to-use colorant.

The colorants according to the invention give intensive dyeings even at physiologically compatible temperatures of below 45.degree. For use on human hair, the colorants can usually be incorporated into an aqueous cosmetic carrier. Suitable hydrous cosmetic carriers are for. As creams, emulsions, gels or surfactant-containing foaming solutions such. As shampoos or other preparations which are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the colorants in anhydrous carrier. Examples of further suitable and inventively preferred ingredients are given below. As a cosmetic carrier according to the invention, in particular an otherwise customary carrier of agents for dyeing human hair is used. Apart from the components according to the invention, the colorants according to the invention may be composed according to known colorants or contain the usual ingredients for them. The agents according to the invention contain the compounds of the formula (I) and the compounds of component B preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to use the dye To integrate 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 according to the invention may additionally contain further organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

On the presence of oxidizing agents, for. B. H ₂ O ₂ , can be dispensed with, especially if the agent according to the invention contains no oxidation dye precursors. If the agent according to the invention contains air-oxidizable oxidation dye precursors or indole or indoline derivatives, oxidizing agent can be dispensed with without problems in such a case. However, it may be desirable to add hydrogen peroxide or other oxidizing agents to the shampooing agents of the present invention which are brighter than the keratinous fiber to be dyed. Oxidizing agents are generally used in an amount of 0.01 to 6 wt .-%, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ . Mixtures of several oxidizing agents, such as a combination of hydrogen peroxide and peroxodisulfates of the alkali and alkaline earth metals or from iodide ion sources, such as alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates, can be used. In summary, agents according to the invention which additionally contain oxidizing agents, in particular H ₂ O ₂ , in an amount of from 0.01 to 6% by weight, based on the application solution, are preferred.

Another object of the present invention is therefore an agent which is characterized in that it is prepared immediately before use by mixing at least two preparations, wherein the at least two preparations are provided in at least two separate prefabricated containers and wherein a container is an agent ( FZ) which contains in a cosmetic carrier at least one dyeing preparation comprising as component A at least one compound of formula (I) and at least as component B a C, H-acidic compound, and another container an oxidizing agent preparation (Ox) containing at least an oxidizing agent.

In order to avoid incompatibilities, however, it is particularly preferred if the dyeing preparation is packaged separately according to component A, containing at least one compound according to formula (I), and component B, containing at least one C, H-acidic compound, and these only immediately be mixed together before use. It may be irrelevant whether component A is first mixed with component B or first with the oxidizing agent preparation (Ox). It is likewise possible first to mix component B with the oxidizing agent preparation (Ox) and then to add component A. The oxidizing agent preparation (Ox) preferably contains as the oxidizing agent hydrogen peroxide and / or one of its solid addition products of organic or inorganic compounds, such as urea, melamine and sodium borate.

Preferably, the amount of oxidizing agent in the ready-to-use agent is 0.1 to 12% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight (calculated as 100% H ₂ O ₂ ), in each case based on the ready-to-use means.

Such oxidizer formulations are preferably aqueous, flowable oxidizer formulations. In this case, preferred formulations are characterized in that the flowable oxidizing agent preparation, based on its weight, 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt .-%, more preferably 60 to 77, 5 wt .-% and in particular 65 to 75 wt .-% water.

According to the invention, however, the oxidation dye can also be applied to the hair together with a catalyst. Such catalysts are z. For example, certain enzymes, iodides, quinones or metal ions. ,

Furthermore, it has proven to be advantageous if the oxidizing agent preparations (Ox) contain at least one stabilizer or complexing agent. Particularly preferred stabilizers are phenacetin, alkali benzoates (sodium benzoate) and salicylic acid. Also preferred according to the invention is the use of so-called complexing agents. Complexing agents are substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents. Complexing agents which are preferred according to the invention are nitrogen-containing polycarboxylic acids, in particular EDTA, and phosphonates, such as hydroxyalkane or aminoalkanephosphonates, in particular 1-hydroxyethane-1,1-diphosphonate (HEDP), ethylenediamine tetramethylenephosphonate (EDTMP) and diethylenetriaminepentamethylenephosphonate (DTPMP) or their sodium salts.

The agents for color change or the dyeing preparation (FZ) and optionally the oxidizing agent preparation (Ox) according to the invention are preferably formulated as flowable preparations.

Preferably, the flowable preparations (FZ) and optionally the oxidizing agent (Ox) is further added an emulsifier or a surfactant, wherein surface-active substances are referred to depending on the field of application as surfactants or as emulsifiers and anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and Emulsifiers are selected. Preferred anionic surfactants are alkyl 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. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine. Preferred amphoteric surfactants are N-cocoalkyl aminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine. Particularly suitable nonionic surfactants are C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. As further preferred nonionic surfactants, the alkylene oxide addition products to saturated linear fatty alcohols and fatty acids with in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid have been found. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants. The anionic, nonionic, zwitterionic or amphoteric surfactants are used in amounts of from 0.1 to 45% by weight, preferably from 1 to 30% by weight and very particularly preferably from 1 to 15% by weight, based on the total amount of the ready-to-use agent ,

Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. The cationic surfactants are contained in the compositions according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

Furthermore, the agents according to the invention may contain further active ingredients, auxiliaries and additives, for example nonionic polymers (such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone, vinylpyrrolidinone / vinyl acetate copolymers, polyethylene glycols and polysiloxanes); Silicones (such as dimethicones or cyclomethicones, polyarylsiloxanes and / or polyalkylarylsiloxanes, amodimethicones, dimethicone copolyols, bis-PEG / PPG-20/20 dimethicones), cationic polymers (such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidinone copolymers, vinylpyrrolidinone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol), zwitterionic and amphoteric polymers (such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / Methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, diallyldimethylammonium chloride / acrylate copolymers, t-butylaminoethyl methacrylate / N- (1,1,3-tetramethylbutyl) acrylamide / acrylate (/ methacrylate) copolymers ), anionic polymers (such as polyacrylic acids, crosslinked polyacrylic acids, vinyla cetate / crotonic acid copolymers, vinylpyrrolidinone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / Nt-butyl acrylamide terpolymers), other thickening agents (such as agar-agar , Guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives such as. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol), structurants (such as glucose, maleic acid and lactic acid), hair conditioning compounds (such as phospholipids, cephalins and silicone oils) , Protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins, fibrous structure-improving active ingredients, in particular mono-, di- and oligosaccharides, defoamers such as silicones, antidandruff active ingredients (such as Piroctone Olamine, zinc omadine and climbazole), amino acids and oligopeptides, in particular arginine and / or serine, light stabilizers (such as derivatized benzophenones, cinnamic acid derivatives and triazines ), Active substances (such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts and bisabolol), plant extracts, fats and waxes such as beeswax, montan wax and paraffins, 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), propellants such as propane-butane Mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants. The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents. With regard to further optional components and 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 additional active ingredients and auxiliaries are preferably used in the agents according to the invention in amounts of from 0.0001 to 10% by weight, in particular from 0.0005 to 5% by weight, based on the total weight of the application mixture.

Dyeing processes on keratin fibers usually take place in an alkaline medium. However, in order to protect the keratin fibers as well as the skin as much as possible, it is not desirable to set too high a pH. Therefore, it is preferred if the pH of the ready-to-use agent is between 6.5 and 10.0, in particular between 7.0 and 9.5. For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ^° C.

To adjust the pH, the skilled artisan uses acidifying and alkalizing agents. Common acidifying agents are dilute mineral acids, in particular dilute hydrochloric acid and dilute sulfuric acid, as well as edible acids, of which citric acid and tartaric acid are particularly preferably used. The alkalizing agents which can be used in the present invention to adjust the preferred pH can be selected from the group consisting of organic alkalizing agents, ammonia, alkali metal hydroxides, alkanolamines, alkali metal metasilicates, alkali metal phosphates and alkali metal hydrogenphosphates. Organic alkalizing agents which can be used according to the invention are preferably selected from alkanolamines of primary, secondary or tertiary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1, 3-diol and triethanolamine, in particular monoethanolamine and triethanolamine. Preferably, the alkanolamines in an amount of 0.05 to 10 wt .-%, in particular from 0.5 to 5 wt .-%, each based on the total weight of the ready-to-use By means of, included. Further organic alkalizing agents which are advantageous according to the invention are basic amino acids which are preferably selected from the group formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine. L-arginine, D-arginine and / or D / L-arginine is particularly preferably used as alkalizing agent in the context of the invention. Inorganic alkalizing agents are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate.

It may be advantageous according to the invention, in particular to avoid irritation of the skin and the mucous membranes, that the agent is low in ammonia, preferably free of ammonia.

The terms "low ammonia" or "ammonia-free" in the context of the invention refer to the amount of ammonia added to the agent, wherein the addition of ammonia take place both as an aqueous, alcoholic, aqueous-alcoholic or other solution and by ammonia gas or by the addition of liquefied ammonia can. However, the addition of ammonia can also be effected by using ammonium salts, the ammonium cation being in equilibrium with its corresponding base, the ammonia itself, depending on the pH of the preparation. The terms "free of ammonia" or "low in ammonia" in the context of the invention therefore also refer to agents which contain ammonium salts in the corresponding amounts. Preferred, low-ammonia agents contain less than 2 wt .-%, in particular less than 0.5 wt .-% and most preferably less than 0.1 wt .-% of added ammonia, each based on the total weight of the application preparation. Ammonia-free in the context of the invention are those agents to which no ammonia has been added by one of the methods described above. Such agents are most preferred.

Another object of the present invention relates to the use of at least one compound according to formula (I) in a component A together with at least one C, H-acidic compound in a component B as coloring components in hair dyes.

In a preferred embodiment, those compounds according to formula (I) are used as a coloring component in hair colorants, which are selected from the preferred and particularly preferred representatives mentioned in the first subject of the invention.

In addition, it may be preferable to additionally use at least one reaction product RP from a compound according to formula (I) and a C, H-acidic compound as coloring component in hair colorants.

Another object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant containing in a cosmetic carrier in a component A at least one compound and in a Component B at least one C, H-acidic compound, applied to the keratin fibers, for an exposure time, preferably from 5 to 45 minutes, more preferably 15 to 30 minutes, left on the fiber and then rinsed again or washed out with a shampoo , During the contact time of the agent on the fiber, it may be advantageous to assist the dyeing process by supplying heat. The heat supply can be done by an external heat source, such as warm air of a hot air blower, as well as, especially in a hair dye on living subjects, by the body temperature of the subject. In the latter case, usually the part to be dyed is covered with a hood. In particular, the temperature during the contact time of 5 to 60 minutes between 10 ⁰ C and 40 ⁰ C, in particular between 20 ⁰ C and 38 ⁰ C.

In this case, the compounds of the formula (I) and the C, H-acidic compounds of component B, in particular their above-mentioned preferred and particularly preferred representatives, as coloring components either simultaneously applied to the hair or in succession, d. H. in a multi-step process, it does not matter which of the components is applied first. The optionally contained ammonium or metal salts may be added to the compounds of formula (I) or the C, H-acidic compounds of component B. Between the application of the individual components can be up to 30 minutes time interval. Pre-treatment of the fibers with the saline solution is also possible.

Before applying the agent according to the invention in the process according to the invention, it may be desirable to subject the keratin-containing fiber to be dyed to a pretreatment. The time sequence of the pretreatment step required for this purpose and the application of the agent according to the invention need not be in immediate succession, but a period of up to a maximum of two weeks may be present between the pretreatment step and the application of the agent according to the invention. For this purpose, several pre-treatment methods are suitable. The fiber V1 is preferably subjected to an oxidative dyeing before the application of the agent according to the invention to a bleaching or V2 before the application of the agent according to the invention. Corresponding processes according to the invention in which the keratin-containing fibers are bleached with a bleaching agent or dyed with an oxidation colorant before a colorant according to the invention is used are preferred.

In pretreatment V1, the keratin-containing fiber is treated with a bleaching agent. The bleaching agent contains, in addition to an oxidizing agent, such as usually hydrogen peroxide, preferably at least one inorganic persalt effective as an oxidation and bleach booster, such as a peroxydisulfate of sodium, potassium or ammonium. Dyes according to the method according to the invention obtained by the pre-treatment V1 a special brilliance and color depth. In the course of pretreatment V2, an agent comprising the aforementioned oxidation dye precursors as developer and optionally coupler components and optionally mentioned derivatives of indole or indoline is applied to the fiber and after an exposure time optionally with the addition of aforementioned suitable oxidizing agents on the hair for 5 to 45 , preferably 10 to 30 minutes left on the Keratinfaser. Thereafter, the hair is rinsed. By the subsequent application of the agent according to the invention existing oxidation dyeings can be given a new shade of shade. If the color shade of the agent according to the invention is selected in the same shade of the oxidative dyeing, then the dyeing of existing oxidation dyeings can be refreshed by the process according to the invention. It turns out that the color refreshing or shading according to the method of the invention is superior to color refreshing or shading alone with conventional substantive dyes in the color brilliance and color depth.

Contains the hair dye in addition to the compounds of formula (I) of component A and the C, H-acidic compounds of component B in addition as an oxidant hydrogen peroxide or a hydrogen peroxide-containing oxidant mixture, the pH of the hydrogen peroxide-containing hair dye is preferably in a pH range from pH 7 to pH 11, more preferably pH 8 to pH 10. The oxidizing agent can be mixed with the hair dye immediately before use and the mixture applied to the hair. If the compounds of the formula I and the component B are applied to the hair in a two-stage process, the oxidizing agent must be used in one of the two process stages together with the corresponding coloring component. For this purpose, it may be preferable to formulate the oxidizing agent with one of the coloring components in a container.

The compounds according to formula (I) of component A and the C, H-acidic compounds of component B can be stored either in separate containers or together in a container, either in a liquid to pasty preparation (aqueous or anhydrous) or as a solid, for example as a dry powder. If the components are stored together in a liquid preparation, it should be substantially anhydrous to reduce a reaction of the components and have an acidic pH. If the components are stored together, it is preferred to formulate these as a solid, in particular in the form of a preferably multilayer molded article, for example as a tablet. In the case of multilayer molded articles, the compounds according to formula (I) of component A are incorporated in one layer and the C, H-acidic compounds of component B in another layer, wherein between these layers preferably a further layer as a release layer. The separating layer is free of compounds of components A and B. In the separate storage, the reactive components are intimately mixed with each other just before use. In dry storage, a defined amount of warm, in particular 30 ⁰ C to 80 ⁰ C, water is usually added prior to application and made a homogeneous mixture.

Another object of the invention is the use of an agent for color change keratinischer fibers, which is obtained by mixing at least two components, wherein the first component (component A) at least one compound according to formula (I) and / or one of its physiologically acceptable salts, and the second component (component B) contains at least one C, H-acidic compound for the nuancing of oxidation colorations of keratin-containing fibers, in particular human hair. In use, it is irrelevant whether the shading occurs simultaneously during the oxidative dyeing, or the oxidative dyeing takes place before the shading.

The dyeings of keratin-containing fibers are known to be exposed to environmental influences, such as light, friction or washes, and may thereby lose brilliance and color depth. In the worst case, if necessary, a nuance shift of the coloring sets in. Such aged dyeings of keratinous fibers, if desired by the user, may be restored to the color state by color refreshment as presented immediately after the initial dyeing. It is according to the invention, for such a color refreshment, to use a combination of a component A containing at least one compound of the formula (I) and of a component B containing at least one C, H-acidic compound.

Another object of the invention is therefore the use of a means for color change keratinischer fibers, which is obtained by mixing at least two components, wherein the first component (component A) at least one compound according to formula (I) and / or one of its physiologically acceptable Salts, and the second component (component B) contains at least one C, H-acidic compound, for color refreshment of keratin-containing fibers dyed with oxidative colorants. With regard to further preferred embodiments of the method according to the invention or the use according to the invention, what has been said about the agents according to the invention applies mutatis mutandis.

A preferred dosage form of the agent according to the invention is a packaging unit (kit-of-parts), which is made up of separately packaged containers

at least one component A containing at least one compound of the formula (I) and / or one of its physiologically tolerated salts,

at least one component B containing at least one C, H-acidic compound,

optionally at least one component C containing at least one reactive carbonyl compound, which may optionally also be formulated together with component A, - And optionally at least one oxidizing agent preparation containing hydrogen peroxide or a solid addition compound of hydrogen peroxide to inorganic or organic compounds.

The multi-component packaging unit (kit-of-parts) preferably additionally contains an instruction manual. In addition, it may be preferred if an application aid, such as a comb, a brush or a brush, and / or personal protective equipment, such as disposable gloves, the kit is attached. With regard to further preferred embodiments of the multi-component packaging unit (kit-of-parts), what has been said about the agents according to the invention applies mutatis mutandis.

A further subject of the invention is 2,3,6,7-tetrahydro-5H- [1,4] oxazino [2,3,4-ij] quinoline-9-carbaldehyde:

Another object of the invention is 2,3,5,6-tetrahydro [1,4] oxazino [2,3,4-hi] indole-8-carbaldehyde:

The following examples are intended to exemplify the invention without, however, limiting it to the scope and scope.

B e i s p e e l e

1. S y e n t i o n e s ia s:

Synthesis of 2, 3, 6, 7-tetrahydro-5H- [1,4] oxazino [2, 3, 4-ij] quinoline-9-carbaldehyde

1st stage: Synthesis of 2,3,6,7-tetrahydro-5H-pyrido [1,2,3-d, e] -1,4-benzoxazine

There were dissolved 17.4 g (0.12 mol) of 8-hydroxyquinoline and 226.8 g (2.40 mol) of chloroacetic acid in 300 ml of tetrahydrofuran. This mixture was cooled by means of a water bath and stirred well. To this mixture was added 20.4 g (0.54 mol) of sodium borohydride in portions over 50 minutes, with the reaction mixture foaming. After the addition was heated to 80 ⁰ C for 3 h. Thereafter, the reaction solution was completely concentrated in vacuo, the residue diluted with 750 ml_ water, neutralized with 8% sodium bicarbonate solution and then extracted three times with 150 to 200 ml_ methyl-ferf-butyl ether. The organic phase was washed with saturated sodium chloride solution, dried over sodium sulfate and then concentrated completely on a rotary evaporator. The intermediate thus obtained was dissolved in 600 ml of 80% aqueous methanol and treated with 50 ml of a 2N sodium hydroxide solution. After 18 hours of stirring at room temperature, the reaction mixture was concentrated in vacuo completely on a rotary evaporator. The residue was diluted with 900 ml of water and the water phase extracted three times with 200 to 250 ml_ methyl-ferf-butyl ether. The organic phase was dried again over sodium sulfate and concentrated completely on a rotary evaporator. The product remained in the form of a dark brown oil. Yield: 9.2 g (44%); ¹ H-NMR (400 MHz, DMSOd ₆ ): δ [ppm] = 1.92 (m, 2H); 2.68 (t, 2H); 3.01 (t, 2H); 3.11 (t, 2H); 4.20 (t, 2H); 6.44 (m, 3H); ¹³ C-NMR (400 MHz, DMSOd ₆ ): δ [ppm] = 21, 5; 26.2; 46.9; 48.2; 64.1; 1 13.0; 116.9; 121, 0; 122.6; 132.7; 143.1.

2nd stage: Synthesis of 2,3,6,7-tetrahydro-5H- [1,4] oxazino [2,3,4- / y] quinoline-9-carbaldehyde (A1)

urotropin

HAc (half conc.) / HCl

To a solution of 9.2 g (0.05 mol) of 2,3,6,7-tetrahydro-5H-pyrido [1,2,3-d, e] -1,4-benzoxazine in 40 ml of half-concentrated acetic acid Added 13.1 g (0.09 mol) of urotropin (hexamethylenetetramine) and the resulting mixture heated at reflux for 3 h. After the reaction mixture was cooled to 60 ⁰ C, 38 ml of semi-concentrated hydrochloric acid solution were added. The light brown reaction mixture was poured onto about 200 ml of ice and stored in the refrigerator overnight, then the precipitated product was filtered off and dried. Yield: 7.3 g (68%); ¹ H-NMR (400 MHz, DMSOd ₆ ): δ [ppm] = 1.91 (m, 2H); 2.75 (t, 2H); 3.24 (t, 2H); 3.37 (t, 2H); 4.19 (t, 2H); 6.98 (s, 1H); 7.10 (s, 1H); 9.53 (s, 1H); ¹³ C-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 20.2; 26.3; 46.9; 48.2; 63.2; 113.2; 120.9; 124.8; 138.7; 142.1; 172.0; 189.5.

2. For use in e p e s e s

Aqueous gel formulation for Component A Gel 1

Aldehyde derivative (A1) 10 mmol

Natrosol HR 250 2 g

NaOH (50%, aqueous solution) possibly a few drops Water, demineralized ad 100 g

The aldehyde (substance A) was dissolved or suspended in a little water. To increase the solubility was alkalized if necessary with a few drops of 50% sodium hydroxide solution. The mixture was then made up to 98 g with water and stirred until complete dissolution of the aldehyde (partially with gentle warming to about 40 ⁰ C). Natrosol was then added with stirring and the swelling process was awaited.

Aqueous gel formulation for component B Gel 2 C, H-acidic compound 10 mmol Natrosol HR 250 2 g water, fully desalted ad 100 g

The C, H-acidic compound (substance B) was first dissolved with stirring in a little water, then made up to 98 g with water. While stirring, the Natrosol was added and the swelling process was awaited.

The two aqueous gel formulations were mixed in the ratio 1: 1, then the pH was adjusted with ammonia or tartaric acid. This ready-to-use hair dye thus obtained was applied to a hair strand of 90% gray, non-pretreated human hair applied (liquor ratio gel mixture / hair = 2: 1) and evenly distributed with an Applicette. After a contact time of 30 minutes at 32 ⁰ C, the tress was rinsed with lukewarm water and then dried in a stream of warm air. The stains were visually assessed under a daylight lamp.

Substance A

A1 2,3,6,7-Tetrahydro-5H- [1,4] oxazino [2,3,4- / y] quinoline-9-carbaldehyde

Substance B

B1 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogen sulfate

B2 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide

B3 1, 2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium p-toluenesulfonate

Color intensity: +++ = high ++ = medium + = bad

Claims

Patent claims

1. agent for color change keratinischer fibers, characterized in that it is obtained by mixing of at least two components, wherein the first component (component A) at least one compound according to formula (I) and / or one of its physiologically acceptable salts

(I) contains, in which

R1 is a hydrogen atom, a C-rC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a hydroxy group, a C ₁ - C ₆ alkoxy group , a C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl group, a halogen atom, a carboxy group, a sulfonic acid group, a C ₁ -C ₆ -alkoxycarbonyl group, a nitrile group, a nitro group, an amino group, a mono- (C 1 -C 4) C ₆ alkyl) amino group, a di (C ₁ -C ₆ alkyl) amino group, an optionally substituted aryl group or an optionally substituted heteroaryl group, and n is a natural number from 2 to 5, and the second component (component B) contains at least one C, H-acidic compound.

2. Composition according to claim 1, characterized in that component A contains at least one compound according to formula (I) and / or one of its physiologically acceptable salts, wherein R 1 is a hydrogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy group , a C ₁ -C ₆ alkoxy group or a halogen atom.

3. Composition according to one of claims 1 to 2, characterized in that component A contains at least one compound according to formula (I) and / or one of its physiologically acceptable salts, wherein n is one of the numbers 2 or 3.

4. Composition according to one of claims 1 to 3, characterized in that the component A as the compound of formula (I) 2,3,6,7-tetrahydro-5H- [1, 4] oxazino- [2,3,4 -ij] quinoline-9-carbaldehyde and / or one of its physiologically acceptable salts.

5. Composition according to one of claims 1 to 4, characterized in that the component B contains as C, H-acidic compound at least one compound selected from the group consisting of compounds of formula (II), ^R5 vV ^R2

R4 '^ * " ^{^} R3 x (H), where

R2 is a Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ -alkoxy-C ₂ -C _6- alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aryl-C ₁ -C ₆ -alkyl group or an optionally substituted heteroaryl-C ₁ -C ₆ -alkyl group,

R3 and R4 each independently represent a hydrogen atom, a Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, an optionally substituted aryl-C | -C ₆ alkyl group, or an optionally substituted heteroaryl-Ci-Cβ-alkyl group, with the proviso that at least one of the substituents R3 and R4 is not hydrogen, and that the substituent on the carbon atom, which is linked to the heterocycle of the formula (II) is, carries at least two hydrogen atoms,

R5 represents a C-rC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a Ci-Ce-hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C-rC ₆ -alkoxy-C ₂ -C ₆ -alkyl group, an optionally substituted aryl-CrC ₆ -alkyl group or an optionally substituted heteroaryl-C ₁ -C ₆ -alkyl group, and X ^'is a physiologically acceptable anion,

from compounds of the formula (III)

I.CN

^H't '~ ^CH * (Hl). wherein

Het is an optionally substituted heteroaromatic and

L is a direct bond or a carbonyl group,

and / or their physiologically acceptable salts.

6. Composition according to claim 5, characterized in that component B contains as C, H-acidic compound at least one compound according to formula (III), wherein the radical Het is derived from a heteroaromatic radical selected from 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 and coumarin, wherein the aforementioned heteroaromatic compounds have at least one group selected from a halogen atom, a nitro group, a thio group, a thio (C -CC ₆ ) alkyl group, a heteroaryl group, an aryl group, a (C-ι-C ₆ ) alkyl group, a (C-ι-C ₆ ) alkoxy group, a hydroxy group, a (C ₂ -C ₆₎ hydroxyalkyl group, a (C ₂ -C ₆₎ -polyhydroxyalkyl group, a _(C-ι-C6) alkoxyl _(C-ι-C6) alkyl group (an aryl C-ι-C ₆₎ alkyl group, an amino group, a mono- (C ₁ -C ₆ -alkyl) amino group, a di- (C ₁ -C ₆ -alkyl) amino group, a dialkylaminoalkyl group - (CH ₂ ) _n -NR'R wherein 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.

7. Composition according to one of claims 1 to 6, characterized in that the component B contains as C, H-acidic compound at least one compound which is selected from the group consisting of salts of 1, 2-dihydro-1 , 3,4,6-tetramethyl-2-oxopyrimidiniums, salts of 1, 2-dihydro-1, 3,4-trimethyl-2-oxopyrimidiniums, salts of 1, 2-dihydro-1, 3,4,6-tetramethyl 2-thioxopyrimidiniums, salts of 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium, salts of 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6 trimethyl-2-oxopyrimidiniums and from 2- (cyanomethyl) benzimidazole.

8. Composition according to one of claims 1 to 7, characterized in that it additionally contains in a component C at least one reactive carbonyl compound which is selected from 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 - hyd, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, coniferic aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy -2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3 -di methyl-benzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 3,5-diethoxy-4-hydroxy-benzaldehyde, 2,6-diethoxy 4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 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-dihydroxybenzaldehyde 6-methyl-benzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 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, A-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodo-benz aldehyde, 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, A-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1 naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-ene nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nit robenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylamino cinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal.

9. Composition according to one of claims 1 to 8, characterized in that the compounds of component A according to formula (I), the C, H-acidic compounds of component B and optionally the reactive carbonyl compounds of component C in each case in a Amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant are included.

10. Composition according to one of claims 1 to 9, characterized in that it color amplifier selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3rd Hydroxypyridine, A-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidinone, Pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine or any mixtures thereof.

11. Composition according to one of claims 1 to 10, characterized in that it has a pH of 6.5 to 10.0, preferably between 7.0 and 9.5.

12. Use of a composition according to any one of claims 1 to 11 for the color refreshment of keratin-containing fibers dyed with oxidative colorants.

13. A process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant according to one of claims 1 to 11 applied to the keratin fibers, for an exposure time, preferably from 5 to 45 minutes, left on the fiber and then rinsed again or with Washed out with a shampoo.

14. 2,3,6,7-Tetrahydro-5H- [1,4] oxazino [2,3,4-ij] quinoline-9-carbaldehyde.

15. 2,3,5,6-Tetrahydro [1,4] oxazino [2,3,4-hi] indole-8-carbaldehyde.