EP2054012A1

EP2054012A1 - Substances for dyeing keratinous fibers

Info

Publication number: EP2054012A1
Application number: EP07803067A
Authority: EP
Inventors: Wibke Gross; Doris Oberkobusch; Ralph Nemitz; Horst Höffkes
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2006-09-05
Filing date: 2007-08-30
Publication date: 2009-05-06
Also published as: CA2662460A1; RU2009112280A; US20100037909A1; WO2008028861A1; DE102006042075A1; AU2007293918A1

Abstract

Disclosed are substances which contain unsaturated, non-aromatic dialdehydes of formula (Ia) and/or the tautomer (Ib) thereof, wherein R1, R2, and R3 are defined as indicated in claim 1, along with at least one CH-acidic compound of formulas (II) and/or (III), wherein R6, R7, R8, R9, R10, Y, X-, Het, and X1 are defined as indicated in claim 1, in a cosmetic carrier. Said substances color keratinous fibers, especially human hair, in an intensive, colorfast, natural brown shade.

Description

"Agent for dyeing keratinous fibers"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains special CH-acidic compounds in combination with unsaturated, non-aromatic dialdehydes, 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.

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

The developer components are usually primary aromatic amines having a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof used.

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

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used.

Suitable coupler substances are, in particular, CC-naphthol, 1,5,7,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4 -Diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4 Chlororesorcinol, 2-chloro-6-methyl-3-anninophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

For other common dye components, reference is expressly made to the series "Dermatology" by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248-250 (Direct-Dye), and Chap. 8, pp. 264-267 (oxidation dyes), as well as the European Inventory of Cosmetic Raw Materials, 1996, published by the European Commission, available in floppy form from the Federal Association of German Industrial and Trade Companies for Pharmaceuticals, Reform Goods and Personal Care, Mannheim ,

Although intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H ₂ O ₂ , which in some cases may result in damage to the fiber. Still problematic is the provision of oxidation hair dyeings in the red region with sufficient fastness properties, in particular with very good washing and rubbing fastnesses.

Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on persons with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage lies in the fact that the dyes often have only insufficient fastness properties.

The object of the present invention is to provide colorants for keratin-containing fibers, in particular human hair, which are at least equivalent in terms of color depth and fastness properties, such as light fastness, rubfastness and washfastness, as well as perspiration and cold wave fastness, to the usual oxidation hair colorants However, necessarily on oxidizing agents such. B. H ₂ O ₂ instructed to be. In addition, the colorants must have no or only a very low sensitizing potential and may under no circumstances be mutagenic.

Colorant containing unsaturated, non-aromatic dicarbonyl compounds according to the following formula Ia or Ib in combination with the selected CH-acidic compounds of the formulas (II) and (III), as well as the use of this combination for dyeing keratin-containing fibers or for color refreshing or shading already dyed keratin-containing fibers are not yet known.

From the patent application W0-A1-2004 / 022016 CH-acidic 1, 2-dihydropyrimidinium derivatives are known, which are suitable in combination with reactive carbonyl compounds, in particular benzaldehyde derivatives, for coloring keratin-containing fibers.

Document W0-A1 -98 / 47473 relates to unsaturated dicarbonyl compounds which are a coloring agent in combination with amines, aromatic hydroxy compounds or CH-acidic compounds.

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.

The production of a brown shade can be achieved by blending different bright shades. It is necessary to use yellow component dyes, red component dyes and blue component dyes together. Due to this mixing procedure, the presence of a large number of dye components in the colorant is unavoidable. Often associated with this are application disadvantages such as, for example, a different absorption capacity of the numerous coloring constituents on differently damaged parts of the hair and a resulting inconsistent color result. Also, a nuance due to different good washing or light fastness of the different dyes used over time may be subject to color shifts that are not desired by the consumer.

All these disadvantages can be circumvented if the desired shade of brown is not achieved by the additive mixture of yellow, red and blue, but can be produced directly by a combination of two.

Surprisingly, it has now been found that with the use of the inventive CH-acid compounds of the formulas (II) and / or (IM) together with the specially selected aldehydes of the formula (Ia) or (Ib) only two components are necessary to achieve very intense and dark shades of brown on the hair. A first object of the invention is an agent for dyeing keratin-containing fibers, in particular human hair, contained in a cosmetic carrier

As component A, at least one unsaturated, non-aromatic dicarbonyl compound according to formula (Ia) and / or its tautomer (Ib),

(Ia) (Ib) in which n is 1 or 2,

R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -alkoxy group, an aryl group, a (C ₁ to C ₆ ) -alkoxy - (d to C ₆ ) alkyl group, wherein in the event that n is 1, the radicals R ¹ and R ³ or R ¹ and R ² or R ² and R ³ , in each case together with the remainder of a five-membered ring, six-membered ring or seven-membered ring, which in turn may be substituted by at least one radical selected from a hydrogen atom, a halogen atom, a (Ci to C ₆ ) - alkyl group, a (Ci to C ₆ ) alkoxy group, an aryl group, a (Ci to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group, together with

• at least one CH-acidic compound as component B, selected from at least one compound according to formula (II) and / or formula

wherein

R ⁶ and R ⁷ are independently a linear or cyclic -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl Ci-C ₆ alkyl group, a Ci- C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C -C alkyl group -Al ₆ -alkoxy-d- C _6, a group R ¹ R ¹¹ N- (CH ₂ ^ -, where R ¹ and R ¹¹ independently represent a hydrogen atom, a dC ₄ alkyl group, a CrC ₄ - Hydroxyalkyl group or an aryl-C-ι-C ₆ alkyl group, wherein R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,

R ⁸ and R ¹⁰ independently of one another represent a hydrogen atom or a C ₁ -C ₆ -

Alkyl group, wherein at least one of the radicals of R ⁸ and R ^{10 is} a dC ₆ alkyl group,

R ⁹ represents a hydrogen atom, a dC ₆ alkyl group, a C ₁ -C ₆ -

Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a dC ₆ alkoxy group, a C-ι-C ₆ -hydroxyalkoxy group, a group R ^m R ^lv N- (CH ₂₎ _q - in which R ^m and R ^IV are independently each other represents a hydrogen atom, a C 1 -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group or an aryl-C 1 -C ₆ -alkyl group, and q represents a number 1,

2, 3, 4, 5 or 6, wherein the radical R ⁹ together with one of the radicals R ⁸ or R ^{10 is} a

5- or 6-membered aromatic ring may form, optionally with a

Halogen atom, a dC ₆ alkyl group, a dC ₆ hydroxyalkyl group, a C ₂ -C ₆ -

Polyhydroxyalkyl group, a dC ₆ alkoxy, a dC ₆ -Hydroxyalkoxygruppe, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _S -, wherein R ^v and R ^vι independently represent a hydrogen atom, a dC _6- alkyl group, a dC ₆ -hydroxyalkyl group or an aryl-dC ₆ -alkyl group and s is a number 0,

1, 2, 3, 4, 5 or 6 may be substituted,

Y represents an oxygen atom, a sulfur atom or a group NR ^V ", in which R ^v " represents a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ -

Alkyl group or a C ₁ -C ₆ -arylalkyl group,

X ^' is a physiologically acceptable anion,

Het is an optionally substituted heteroaromatic and

X ¹ represents a direct bond or a carbonyl group.

The term "non-aromatic" in the sense of the invention means that the carbonyl groups of the dicarbonyl compound according to formulas (Ia) and (Ib) and the preferred embodiments of these formulas (vide infra) do not bind directly to an aromatic.

As CH-acidic compounds are generally considered those compounds which carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond is effected. In principle, there are no limits to the choice of CH-acidic compounds, as long as, after the aldol condensation with a carbonyl compound, in particular with the non-aromatic aldehyde contained in the agents according to the invention, a compound visibly colored to the human eye is obtained.

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.

Compounds of the formula (Ia) or (Ib) which are preferred according to the invention are those in which n is 1 in said formulas.

It is inventively preferred that, when according to formula (Ia) or (Ib) n is 1, the radicals R ¹ and R ³ together with the remainder of the molecule form a five-membered, six-membered or seven-membered ring, which in turn may be substituted by at least one radical may be selected from a hydrogen atom, a halogen atom, a (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) alkoxy group, an aryl group, a (C ₁ to C ₆ ) alkoxy (C-ι to C ₆ ) alkyl group. In this case, it is again preferred according to the invention if the agent contains as compound of the formulas (Ia) or (Ib) at least one compound of the formulas (Ia-1) and / or their tautomer (Ib-1),

wherein

R ² , R ⁴ and R ⁵ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -alkoxy group, an aryl group, a (C ₁ to C ₆ ) -Alkoxy- (C-1 to C ₆ ) alkyl group and the cycle A is a five-membered, six-membered or seven-membered ring.

The cycle A may be carbocyclic or heterocyclic, with a carbocyclic cycle A being preferred according to the invention. Very particularly preferably, the compositions according to the invention contain at least one unsaturated, non-aromatic dicarbonyl compound of the formulas (Ia-2) and / or (Ib-2) and / or (Ia-3) and / or (Ib-3)

(la-2) (lb-2)

(la-3) (lb-3) wherein

R ² , R ⁴ and R ⁵ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -alkoxy group, an aryl group, a (C ₁ to C ₆ ) -Alkoxy- (C-1 to C ₆ ) alkyl group.

According to formulas (Ia), (Ib), (Ia-1), (Ib-1), (Ia-2), (Ib-2), (Ia-3), (Ib-3), it is preferred that R ^{2 represents} a hydrogen atom, a halogen atom (especially chlorine or bromine), a (C ₁ to C ₆ ) alkoxy group or a (C ₁ to C ₆ ) alkyl group, more preferably when R ^{2 is} a hydrogen atom or a halogen atom (especially chlorine or bromine).

According to formulas (Ia-1), (Ib-1), (Ia-2), (Ib-2), (Ia-3), (Ib-3), it is preferred that R ⁴ and R ^{5 are} independently Represents a hydrogen atom, a hydroxy group, a (C ₁ to C ₆ ) alkyl group or a (C ₁ to C ₆ ) hydroxyalkyl group. In this case, it is again preferred if at least one of R ⁴ or R ^{5 is} a hydrogen atom and the other is a hydrogen atom, a hydroxy group, a (C ₁ to C ₆ ) -alkyl group or a (C ₁ to C ₆ ) -hydroxyalkyl group means.

It is preferred according to the invention that as component A according to formula (Ib) at least one of the following compounds or their tautomer (Ia) is present in the composition according to the invention: 2-chloro-3- (hydroxymethylene) cyclohex-1-en-1-carbaldehyde

2-Chloro-3- (hydroxymethylene) -5-methylcyclohex-1-en-1-carbaldehyde

2-Chloro-3- (hydroxymethylene) -6-methylcyclohex-1-en-1-carbaldehyde

3- (hydroxymethylene) cyclohex-1-en-1-carbaldehyde

3- (hydroxymethylene) -5-methylcyclohex-1-en-1-carbaldehyde

3- (Hydroxynethylene) -6-methylcyclohex-1-en-1-carbaldehyde

2-chloro-3- (hydroxymethylene) cyclopent-1-en-1-carbaldehyde

3- (Hydroxymethylene) cyclopent-1-en-1-carbaldehyde

Equivalent to the compounds of formula II are their enamine forms. With the aid of a base, the corresponding enamines can be specifically prepared from the compounds according to formula II by deprotonation on the α-carbon atom of the C 1 -C ₆ -alkyl radicals R ⁸ or R ¹⁰ . By way of example, this deprotonation is illustrated below, wherein for clarification R ⁸ as the radical R-CH ₂ - was chosen. A compound according to the formula IIa is an example of an inventive enamine form of 1, 2-dihydro-pyrimidinium derivatives.

(IIa)

At least one group R ⁸ or R ¹⁰ according to formula II necessarily stands for a C 1 -C ₆ -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its α-carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R ⁸ and R ¹⁰ independently of one another represent hydrogen or a methyl group, where at least one group R ⁸ or R ¹⁰ denotes a methyl group.

In a preferred embodiment, according to formula (II) Y is an oxygen or a sulfur atom, more preferably an oxygen atom.

The radical R ⁶ of the formula (II) is preferably selected from a (C ₆₎ alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ alkenyl group (particularly an allyl group), a hydroxy (C ₂ - to C ₆ ) -alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group.

R ^{9 of} the formula (II) is preferably a hydrogen atom.

Particularly preferred in formula (II) is at least one of R ⁸ and R ^{10 is} a methyl group and the other of these radicals is a hydrogen atom or a methyl group, the radical R ^{9 is} a hydrogen atom, Y is an oxygen or a sulfur atom and Radicals R ⁶ and R ⁷ are independently selected from a (C ₁ -C ₆ ) -alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ -alkenyl group (in particular an allyl group), a hydroxy- (C ₂ -C ₆ ) alkyl group, especially a 2-hydroxyethyl group, or an optionally substituted benzyl group. 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 the

1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium,

1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,

1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidiniums,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and

1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium.

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 ^' .

The radical Het according to the formula (III) preferably represents the molecule fragment of the formula (V) wherein

R ¹¹ and R ¹² are each independently hydrogen, hydroxy, halogen, nitro, linear or cyclic dC ₆ alkyl, C ₂ -C ₆ alkenyl, optionally substituted aryl, cyanomethyl, cyanomethylcarbonyl , an optionally substituted heteroaryl group, an aryl _C-ι-C6 alkyl group, a C-ι-C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a dC ₆ alkoxy group, a dC ₆ alkoxycarbonyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, a dC ₆ -Sulfoalkylgruppe, a dC ₆ -Carboxyalkylgruppe, a group R ^vm R ^lx N- (CH ₂ ) _m -, wherein R ^vι "and R ^ιx independently represent a hydrogen atom, a linear or cyclic dC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a dC ₆ hydroxyalkyl group, or an aryl-dC ₄ alkyl group, wherein R ^VI "and R together with the nitrogen atom ^ιx can form a 5-, 6- or 7-membered ring and m is a number 0, 1, 2, 3 or 4, wherein R ¹¹ and / or R ^{12 may form} a fused to the ring of the remainder of the molecule, optionally substituted aromatic or heteroaromatic, 5- or 6-ring

X ² and X ³ independently of one another represent a nitrogen atom or a group CR ¹³ , where R ¹³ is a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ - C ₆ alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl, an optionally substituted heteroaryl group, an aryl Ci-C ₆ alkyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C -C ₆ alkoxy group, a Ci-C ₆ alkoxycarbonyl group, a Ci -C ₆ -alkoxy-C ₂ -C ₆ - alkyl group, a Ci-C ₆ sulfoalkyl group, a Ci-C ₆ carboxyalkyl group and a group R ^x R ^xl N- (CH ₂₎ _n -, wherein R ^x and R ^xι independently represent a hydrogen atom, a linear or cyclic Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ - Hydroxyalkylgruppe or an aryl-dC ₄ alkyl group, wherein R ^x and R ^xι together with the Nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 0, 1, 2, 3 or 4, wherein at least one of the substituents X ² and X ³ together with the remainder of a fused optionally substituted aromatic 5 - or can form 6-ring,

X ⁴ represents an oxygen atom, a sulfur atom, a vinylene group or a group N-H, where the latter two groups independently of one another optionally together with a linear or cyclic dC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl C-ι-C ₆ alkyl group, a C ₂ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, a C ₁ -C ₆ -sulfoalkyl group, a dC ₆ -carboxyalkyl group, a group R ^X "R ^XI " N - (CH ₂₎ _P -, wherein R ^x 'and R ^xι "are independently a hydrogen atom, a linear or cyclic dC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C-ι-C ₆ - Hydroxyalkyl group or an aryl-C-ι-C ₄ -alkyl group, wherein R ^x "and R ^xι " together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p is a number 0, 1, 2 , 3 or 4, may be substituted,

with the proviso that when X ^{4 is} a vinylene group, at least one of X ² or X ^{3 represents} a nitrogen atom.

The bond of the heterocyclic ring according to formula (V) to the molecule fragment -X ¹ -CH ₂ -C≡N to give the compound according to formula (IM) according to the invention takes place at the ring of the heterocycle and replaces a hydrogen atom bound to this ring. Consequently, it is imperative that the substituents R, R, X, X and X of the formula (V) must be selected such that at least one of these substituents allows a corresponding bond formation. Thus, it is compulsory that in formula (V), at least one of R ¹¹ or R ^{12 form} the bond to the molecular fragment -X ¹ -CH ₂ -C≡N when X ^{4 is} an oxygen atom or a sulfur atom and X ² and X ^{3 represents} a nitrogen atom.

The radical Het of the formula (V) is particularly preferably derived from the heteroaromatics 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, benzothiazole , Phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine and coumarin, wherein the aforementioned heteroaromatic compounds having at least one group selected from a halogen atom, a nitro group, a thio group, a ThJo - (C ₁ -C ₆ ) - alkyl group, a heteroaryl group, an aryl group, a (C-ι-C ₆ ) alkyl group, a (C ₁ -C ₆ ) - alkoxy group, a hydroxy group, a (C ₂ -C ₆ ) -Hydroxyalkylgrup pe, a (C ₂ -C ₆ ) - polyhydroxyalkyl group, a (C-rC ^ -alkoxyl ^ C-rC ^ alkyl group, an aryl (C-ι-C ₆ ) - alkyl group, an amino group, a (C ι-C ₆ ) -monoalkylamino group, a (C ₁ -C ₆ ) - Dialkylamino group, a dialkylaminoalkyl group - (CH ₂ ) _n -NR'R ", wherein n is an integer of 2 and 6 and R 'and R" independently represents a linear or branched alkyl group, which may optionally together form a ring substituted could be.

Preferably, the compounds of the formula (III) are selected from at least one compound 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-trimethylpyrrol-3-oyl) -acetonitrile, 1 / - / - benzimidazol-2-ylacetonitrile, 1 / - / - Benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2 -Methyl-indol-3-oyl) -acetonitrile, δ-cyanoacetyl-T-methoxy-methylcoumarin, 2- (2-isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl- 5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumaron-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) 2,3-dihydro-1-benzofuran-2-carboxylic acid tert-butyl ester, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl -1,4-dihydrothiochromeno ^ .S-cypyrazole-S-oxy-acetonitrile. Particularly preferred is 1 / - / - benzimidazol-2-ylacetonitrile [2- (cyanomethyl) benzimidazole].

Very particularly preferred agents according to the invention are characterized in that they contain as component B at least one CH-acidic compound selected from

Salts of 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium,

Salts of 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium,

Salts of 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium,

Salts of 1-allyl-i, 2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,

Salts of 1, 2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidiniums or

2- (cyanomethyl) benzimidazole, or mixtures of more than one of these CH-acidic compounds.

In a second embodiment, it may be advantageous for extending the color spectrum to add at least one further compound as component C in addition to at least one compound of formula (Ia) or (Ib) as component A and at least one compound of component B. This compound of component C is selected from CH-acidic compounds other than compounds of formulas (II) and (III). It proves to be advantageous according to invention, if in addition at least one CH-acidic compound is contained as component C, which is selected from at least one compound of the group consisting of physiologically acceptable anions, in particular p-toluenesulfonates, methanesulfonates, hydrogen sulfates, tetrafluoroborates and Halides such as the chlorides, bromides and iodides, formed salts of 1, 4-dimethylchinolinium, 1-ethyl-4-methyl-quinolinium, 1-ethyl-2-methylquinolinium, 1, 2,3,3-tetramethyl-3H-indolium , 2,3-Dimethyl-benzothiazoliums, 2,3-dimethyl-naphtho [1,2-d] thiazoliums, 3-ethyl-2-methyl-naphtho [1,2-d] thiazoliums, 3-ethyl-2-methyl benzoxazolium, 1,2,3-trimethylquinoxaluminum, 3-ethyl-2-methyl-benzothiazolium, 2,5-dimethyl-3- (2-propenyl) -1, 3,4-thiadiazolium, 3-ethyl-2,5 - Dimethyl-1, 3,4-thiadiazoliums, 1, 2-dimethylchinolinium and 1, 3,3-trimethyl-2-methylenindoline (Fischer's base), and oxindole, 3-methyl-1-phenyl-pyrazoline 5-one, indan-1, 2-dione, indan-1, 3-dione, indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 4,5-dihydro-4 -imino-2- (1-piperidinyl) thiazole (hydrochloride), 4,5-dihydro-4-imino-2- (4-morpholinyl) thiazole (hydrochloride), 4,5-dihydro-4-imino-2 - (1-pyrrolidinyl) thiazole (hydrochloride).

In a next embodiment, it may be advantageous for extending the color spectrum to add at least one further reactive carbonyl compound as component D to the inventive compositions in addition to at least one compound according to component A and at least one compound of component B. It is also possible, in addition to at least one compound according to component A, at least one compound of component B and at least one further reactive carbonyl compound as component D to add at least one additional CH-acidic compound of component C (vide supra)

Reactive carbonyl compounds as component D in the context of the invention have at least one carbonyl group as a reactive group which reacts with the CH-acidic compound according to component A and or optionally further CH-acidic compounds present to form a carbon-carbon bond. Preferred reactive carbonyl compounds are aldehydes and ketones. Furthermore, according to the invention, those compounds are also usable as component D in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the CH-acidic 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 or ketals as addition compound c) of water to form hydrates as addition compound (component C is derived in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred additional reactive carbonyl compounds of component D are listed below. Here, preferred agents according to the invention additionally comprise, as component D, at least one reactive carbonyl compound which is selected from among those selected from benzaldehyde and its derivatives, cinnamic aldehyde and its derivatives, naphthaldehyde and its derivatives, 5- (4-dimethylaminophenyl) penta-2 , 4-dienal, 5- (4-

Diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-

Dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-

Piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) -penta-2,4-dienal, 5- (4-

Pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3 , 5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- ( 4

Pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3 Acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, A-formyl-1-methylpyridinium -, 2-Formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, A-formyl -1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methyl-quinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium-, 2- Acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1 -methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl -1-benzylchinolinium- , 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6-formyl-1-allylquinolinium, 7-formyl-1-allylquinolinium and 8-formyl-1 allyl quinolinium, 5-acetyl-1-methylquinolinium, 6-acetyl-1-methylquinolinium, 7-acetyl-1-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6- Acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium , δ-acetyl-1-benzyl-quinolinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl-1-allyl-quinolinium and 8-acetyl-1-allyl-quinolinium, 9-formyl-1-oxide methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'-formylphenyl) benzimidazolium, 1, 3-dimethyl-2- (4'-formylphenyl) - imidazolium, 2- (4'-Formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3-methylbenzoxazoline, 2- (5'-formyl) 2'-furyl) -3-ethylbenzothiazolinyl, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-ethylbenzothiazolinyl, 2 ' - (3'-Formylphenyl) -3-methylbenzothiazolinyl, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2 - (4'

Formylphenyl) -3,5-dinethylbenzothiazolene benzenesulfonate, p-toluenesulfonate, methanesulfonate, - perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1- Methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfoisoisine, 5-carboxyisatin, Chinisatin, 1-Methylchinisatin, and any mixtures of the above compounds.

Benzaldehyde and / or cinnamaldehyde and / or naphthaldehyde and their derivatives, in particular with one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as additional aromatic aldehyde of component D in the compositions according to the invention. Again, the compounds according to formula (D-1) are preferred,

in which

R ¹ , R ² and R ³ are each independently hydrogen, halogen, dC ₆ alkyl, hydroxy, dC ₆ alkoxy, formyl, (C ₂ -C ₆ ) alkenyl, C -ι-C ₆ dialkylamino group, a di (C ₂ -C ₆ - hydroxyalkyl) amino group, a di (C-ι-C ₆ -alkoxy-C-ι-C ₆ alkyl) aminoguppe, a C ₁ -C ₆ Hydroxyalkyloxy group, a sulfonyl group, a carboxy group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group or a nitro group,

Z 'is a direct bond or a vinylene group,

R ⁴ and R ⁵ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring. Here again preferred agents according to the invention are characterized in that the aromatic aldehyde (s) is / are selected from 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1 naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo- 4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylannino-2- methoxybenzaldehyde, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, A-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, A-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4- hydroxy-2,6-dimethy l-benzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2 Ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2, 4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-

Dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy- 3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehyde, 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-methoxy-benzaldehyde, 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-dimethylannino-2-hydroxybenzaldehyde, A-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxybenzaldehyde 3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro r-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-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, A-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxybenzaldehyde 5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2 nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-

Dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5- Bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-

Dimethylaminobenzaldehyde, 2-chloro-4-dimethylanninobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-tinaldehyde, 4-dibutylaminobenzaldehyde, A-diphenylaminobenzaldehyde, 4- (1-imidazolyl) -benzaldehyde and piperonal, 5- Formyl 2-hydroxybenzoic acid (3-carboxy-4-hydroxybenzaldehyde), 5-formyl-2-hydroxy-3-methoxybenzoic acid (5-carboxyvanillin), 5-formyl-2-hydroxy-3-methylbenzoic acid (3-carboxy-4-) hydroxy-5-methylbenzaldehyde), 3-ethoxy-5-formyl-2-hydroxybenzoic acid (3-carboxy-5-ethoxy-4-hydroxybenzaldehyde), 3-allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5- methoxybenzaldehyde, 3-allyl-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3- Allyl-4,5-dihydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-nitrobenzaldehyde, 3-Allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-) hydroxybenzoic acid), 5-allyl-4-hydroxyisophthalaldehyde.

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 (Ia) or (Ib) 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 of formula (Ia) or (Ib) of about 1: 1 to about 2: 1 may be useful.

The abovementioned compounds of component A, component B, component C and component D are each preferably used in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant. Corresponding compositions according to the invention, in which the compounds of component A, the Compounds of component B and optionally the compounds of components C and D in each case 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

In addition, the agents according to the invention may additionally contain as oxidation dye precursor at least one developer component and optionally at least one coupler component.

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

)

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C 1 -C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ -C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C 1 -C ₄ ) -alkyl radical or a C ₁ -C ₄ -alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkylrest, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ - acetylaminoalkoxy, a C ₁ - to C ₄ - Mesylaminoalkoxyrest or a C ₁ - to C ₄ - carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ bis mentioned as substituents in the compounds according to the invention C ₄ alkyl radicals are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are especially the amino groups, C ₁ - to C ₄ - monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ -Trialkylammoniumgruppen, C ₁ - to C ₄ -Monohydroxyalkylaminogruppen, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2 -methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (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- (β-Acety laminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine and 5,8-Diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particularly preferred according to the invention p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-

Dihydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups. Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may optionally be substituted by one or more hydroxyl or C ₁ - to C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the proviso that the compounds of the formula (E2) contain only one bridging Y per molecule.

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

Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis- (β-) hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropane-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis- ( 4'-aminophenyl) ethylenediannine, N, N'-bis (4-aminophenyl) tetrannethylenediannine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetrannethylenediannine , N, N'-bis (4-methyl-anninophenyl) -tetramethylenediamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-naphthylphenyl) -ethylenediannine, bis (2 - hydroxy-5-aminophenyl) ethane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N - (4'-aminophenyl) -p-phenylenediannine and 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

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

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, a hydroxy (C-ι- to C ₄ ) -alkylamino, a C ₁ - to C ₄ -Hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl- (C ₁ -C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -alkylamino) - (C 1 -C ₄ ) -alkyl, and

G ¹⁴ is a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy (C 1 -C ₄ ) -alkyl radical, a C ₁ -C ₄ -aminoalkyl radical or a C ₁ -C ₄ -cyanoalkyl radical,

G ¹⁵ is hydrogen, C ₁ - to C ₄ -alkyl, C ₁ - to C ₄ -monohydroxyalkyl, C ₂ - to C ₄ -polyhydroxyalkyl, phenyl or benzyl, and

G ¹⁶ is hydrogen or a halogen atom. The substituents used in formula (E3) are defined according to the invention analogously to the above statements.

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

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

Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

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

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in Offenlegungsschrift WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4- Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2.5, 6-triaminopyrimidine. Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-1-naphthylpyrazole, 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-naphthylpyrazole, 4,5-diamino-3-tert-butyl-1-naphthylpyrazole, 4,5-diamino-1-tert-butyl-3-naphthylpyrazole, 4, 5-Diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-naphthylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) -pyrazole , 4,5-diamino-1-ethyl-3-hydroxynethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-naphthylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3 N-ethyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) -annino-1,3-dinethylpy razol,

3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylanninopyrazole, and 3,5-diamino-4- (β-hydroxyethyl) -annino 1-nnethylpyrazol.

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

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy (C-ι- to C ₄ ) alkyl, a C ₁ - to C ₄ - aminoalkyl, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ - to C ₄ ) -alkylamino- (C-ι- to C ₄ ) -alkyl radical, a di - [(C-ι- to C ₄ ) alkyl] - (C-ι- bis C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C-ι- to C ₄ ) -aminoalkyl, the X radicals are independently a hydrogen atom, a C ₁ - to C ₄ - alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl, a C ₂ - to C ₄ - polyhydroxyalkyl, a C ₁ - to C ₄ -Aminoalky lrest, a (C ₁ - to C ₄ ) -alkylamino- (C 1 -C ₄ ) -alkyl radical, a di - [(C 1 -C ₄ ) -alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, wherein the dialkyl radicals optionally have a carbon cycle or a heterocycle with 5 or 6 chain members , form a C ₁ - to C ₄ hydroxyalkyl or a di- (C ₁ - to C ₄ hydroxyalkyl) -anninoalkylrest, an amino group, a C ₁ - to C ₄ -alkyl- or di- (C ₁ - to C ₄ -hydroxyalkyl) -anninoride, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0 when p + q is 2, n is 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E4) may be mentioned in particular:

Pyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine;

3-aminopyrazolo [1,5-a] pyrimidin-7-ol;

3-aminopyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;

2- (7-aminopyrazolo [1,5-a] pyrimidin-3-yl-amino) -ethanol;

2 - [(3-Anninopyrazolo [1,5-a] pyrinnidin-7-yl) - (2-hydroxy-ethyl) -annino] -ethanol;

2 - [(7-aminopyrazolo [1,5-a] pyrinnidin-3-yl) - (2-hydroxy-ethyl) -annino] -ethanol;

5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diannine;

2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diannine;

3-amino-7-dinethyl-amino-2,5-dinethyl-pyrazolo [1,5-a] pyridine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

The pyrazolo1, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.

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

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 Methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro 6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 6-Dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'- Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4 Dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) -propane, 1- Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3 Bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy 5-n-phenyl-phenyl} -annino) -ethanol, 2 - ({3 - [(2-

Hydroxyethyl) amino] -2-n-ethoxy-5-methylphenyl} -annino) -ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxyethoxy) -5-methyl-phenylannin and 1- Amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylannino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy 4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrinnidine, 4-amino-2,6-dihydroxypyrinnidine, 2,4-diamino-6-hydroxypyrinnidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-naphthylpyrinnidine, 2-amino-4-hydroxy 6-methylpyrinnidine and 4,6-dihydroxy-2-methylpyrinnidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-ethylenedioxybenzene and 1- (2'-hydroxyethyl) -amino 3,4-Nnethylenedioxybenzol and their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-naphthylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-anninophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine. In addition, in a fifth embodiment as precursors of naturally-analogous dyes, preference is given to using such indoles and indolines in the compositions according to the invention which have at least one hydroxyl or amino group, 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 second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula VIa,

in the independently of each other

G ²¹ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxy-alkyl group,

G ²² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

G ²³ is hydrogen or a C 1 -C ₄ -alkyl group,

G ²⁴ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-G ²⁶ in which G ²⁶ is a C 1 -C ₄ -alkyl group, and

G ²⁵ represents one of the groups mentioned under G ²⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,

N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

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 in particular the 5,6-dihydroxyindoline.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula VIb,

(VIb)

in the independently of each other

G ²⁷ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

G ²⁸ is hydrogen or a -COOH group, wherein the -COOH group also as

May be salt with a physiologically acceptable cation,

G ²⁹ is hydrogen or a C 1 -C ₄ -alkyl group,

G ³⁰ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-G ³² in which G ³² is a C 1 -C ₄ -alkyl group, and

G ³¹ stands for one of the groups mentioned under G ³⁰ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

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

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. 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 .-%. 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 u. It may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the invention for achieving the shades that are lighter than the keratin-containing 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.

The oxidizing agent or the oxidizing agent combination can be used according to the invention in conjunction with oxidation catalysts in the hair dye. Oxidation catalysts are, for example, metal salts, metal chelate complexes or metal oxides, which allow a slight change between two oxidation states of the metal ions. Examples are salts, chelate complexes or oxides of iron, ruthenium, manganese and copper. Other possible oxidation catalysts are enzymes. Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose,

- glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

Alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts, Tyrosinase oxidase and tyrosine,

Uricase and uric acid or their salts,

- choline oxidase and choline,

- amino acid oxidase and amino acids.

In a further embodiment, the colorants according to the invention for further modifying the color shades in addition to the compounds according to the invention additionally contain conventional substantive dyes, such as nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those under the international designations or HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52, Basic Blue 6, CI -No. 51, 175; Basic Blue 7, Cl-No. 42.595; Basic Blue 9, Cl-No. 52.015; Basic Blue 26, Cl-No. 44.045; Basic Blue 41, Cl-No. 11, 154; Basic Blue 99, Cl-No. 56.059; Basic Brown 4, Cl-No. 21, 010; Basic Brown 16, Cl-No. 12.250; Basic Brown 17, Cl-No. 12,251; Basic Green 1, Cl-No. 42.040; Basic Orange 31; Basic Red 2, Cl-No. 50.240; Basic Red 22, Cl-No. 11, 055; Basic Red 46; Basic Red 51; Basic Red 76, Cl-No. 12.245; Basic Violet 1, Cl-No. 42.535; Basic Violet 2; Basic Violet 3, Cl- No. 42.555; Basic Violet 10, Cl-No. 45.170; Basic Violet 14, Cl-No. 42.510; Basic Yellow 57, Cl-No. 12.719; Basic Yellow 87 and / or the anionic (acidic) dyes, and / or the nonionic dyes, preferably Acid Black 1, Cl-No. 20.470; Acid Black 52; Acid Blue 7; Acid Blue 9, Cl-No. 42.090; Acid Blue 74, Cl-No. 73.015, Acid Red 18, Cl-No. 16.255; Acid Red 23; Acid Red 27, Cl-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, Cl-No. 45,380; Acid Red 92, Cl-No. 45,410; Acid Orange 3; Acid Orange 7; Acid Violet 43, Cl-No. 60.730; Acid Yellow 1, Cl-No. 10.316; Acid Yellow 10; Acid Yellow 23, Cl-No. 19,140; Acid Yellow 3, Cl-No. 47.005; Acid Yellow 36; D & C Brown no. 1, Cl-No. 20.170 (Acid Orange 24); D & C Green no. 5, Cl-No. 61, 570 (Acid Green G); D & C Orange No. 4, Cl-No. 15.510 (Acid Orange II); D & C Orange No. 10, CI-No. 45.425: 1 (Solvent Red 73); D & C Orange No. 11, Cl-No. 45.425 (Acid Red 95); D & C Red No. 21, Cl-No. 45.380: 2 (Solvent Red 43); D & C Red No. 27, Cl-No. 45.410: 1 (Solvent Red 48); D & C Red No. 33, Cl-No. 17,200 (Acid Red 2A, Acid Red B); D & C Yellow No. 7, CI-No. 45.350: 1 (Solvent Yellow 94); D & C Yellow No. 8, Cl-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, Cl-No. 14,700 (Food Red 4); FD & C Yellow No. 6, Cl-No. 15,985 (Food Yellow 3); Food Green 3; Pigment Red 57-1; Disperse Black 9; Disperse Blue 1; Disperse Blue 3; Disperse Violet 1; Disperse Violet 4; HC Orange 1; HC Red 1; HC Red 3; HC Red 13; HC Yellow 2; HC Yellow 4 known compounds and 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (ß- hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-

Hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Preferred agents according to the invention are characterized in that they additionally contain at least one substantive dye, preferably in an amount of from 0.01 to 20% by weight, based on the total colorant.

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

(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called.

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

CH ₃ SO ₄ ^"

(DZ1) (Basic Yellow 87)

Cl ^"

(DZ2)

(DZ3) (Basic Orange 31)

(DZ5) (Basic Red 51)

(DZ6)

The compounds of the formulas (DZ1), (DZ3) and (DZ5) 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 particularly preferred substantive dyes.

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

Furthermore, the preparations according to the invention may also contain naturally occurring dyes such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, seder and alkano root. It is not necessary that the optionally contained substantive dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, eg. As toxicological, must be excluded.

To obtain further and more intense colorations, the compositions according to the invention may additionally contain color enhancers. The color enhancers are preferably selected from at least one compound of the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, A-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine, their 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 agents according to the invention may have a pH of from pH 4 to 12, preferably from pH 5 to 10.

The colorants according to the invention give intensive dyeings even at physiologically compatible temperatures of below 45 ^° C. They are therefore particularly suitable for dyeing human hair. 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. Examples further suitable and inventively preferred ingredients are given below.

The agents according to the invention contain the compounds of component A 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. 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 3 to 70% by weight of a C ₁ -C ₄ -alkoxy, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

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 so that agents according to the invention which additionally contain anionic, zwitterionic or nonionic surfactants are preferred.

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 as. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 C-men men. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanol ammonium salts with 2 or 3 C atoms in the alkanol group,

linear fatty acids with 10 to 22 carbon atoms (soaps),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16, acylsarcosides having 10 to 18 C Atoms in the acyl group, Acyltaurides having 10 to 18 C atoms in the acyl group,

Acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 C atoms, linear α-olefin sulfonates having 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene glycol ethers according to

DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols which are adducts of about 2 to 15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

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

Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ₃ ⁽⁾ group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid anhydride derivative known by the CTFA designation Cocamidopropyl Betaine. Ampholytic surfactants are surface-active compounds which, apart from a C ₈ -i ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or _-SO3H group and are capable of forming inner 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 with each about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _12-i ₈ acyl sarcosine.

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

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and on

Alkylphenols having 8 to 15 C atoms in the alkyl group,

C _{_12-22} fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol,

C _{_8-22} alkyl mono- and oligoglycosides and ethoxylated analogs thereof,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters

Addition products of ethylene oxide to fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. 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, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80.).

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

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the methyl hydroxyalkyl marketed under the trademark Stepantex ^® dialkoyloxyalkylammoniummethosulfate.

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

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

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 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.

Further active agents, auxiliaries and additives are, for example, nonionic polymers such as, for example, 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-dimethyldiallylammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinylalcohol, zwitterionic and amphoteric polymers such as acrylamidopropyl -trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / Butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, thickeners such as agar-agar, guar gum, alginates, xanthan gum , Gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. As polyvinyl alcohol, structurants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, such as soybean lecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine, other pH adjusters such as ammonia, monoethanolamine, basic amino acids and citric acid

Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

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

Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,

Pearlescing agents such as ethylene glycol mono- and distearate,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and antioxidants.

The constituents of the water-containing carrier are used to prepare the colorants according to the invention in amounts customary for this purpose; z. B. emulsifiers in concentrations of 0.5 to 30 wt .-% and thickening agents in concentrations of 0.1 to 25 wt .-% of the total colorant used.

For the dyeing result, it may be advantageous to add ammonium or metal salts to the colorants. Suitable metal salts are, for. As formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals such as potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, Strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, with sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred. These salts are preferably contained in an amount of 0.03 to 10 wt .-%, in particular from 0.5 to 5 wt .-%, based on 100 g of the total ready colorant.

The pH of the ready-to-use dyeing preparations is usually between 2 and 11, preferably between 5 and 10.

Another object of the present invention relates to the use of at least one compound according to formula (Ia) and / or its tautomer (Ib),

(Ia) (Ib) as component A, wherein R ¹ , R ² and R ^{3 are} as defined in the first subject of the invention, together with at least one CH-acidic compound of the formulas (II) and / or (IM) as component B

wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Y, X ^" , Het and X ^{1 are} as defined in the first subject of the invention,

as a coloring component in hair dyes.

In a preferred embodiment, those compounds according to component A and compounds of component B 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.

A third 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 at least one compound according to formula (Ia) and / or its tautomer (Ib) as

Component A,

(Ia) (Ib) wherein R ¹ , R ² and R ^{3 are} as defined in the first subject of the invention together with at least one CH-acidic compound of formulas (II) and / or (IM) as component B

wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Y, X ^" , Het and X ^{1 are} as defined in the first subject of the invention, Applied to the keratin fibers, some time, usually about 15-30 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 this case, the compounds of component A and the compounds of component B, in particular their above-mentioned preferred and particularly preferred representatives, as coloring components either simultaneously applied to the hair or else 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 can be added to the compounds of component A or the 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 there may be a period of up to a maximum of two weeks 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 is preferred

V1 before the application of the bleaching agent according to the invention or V2 before the use of the oxidative staining agent according to the invention

subjected.

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 context of pretreatment V2, an agent containing 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 a contact time optionally with the addition of aforementioned suitable oxidizing agents on the hair for 5-45 minutes leave the keratin fiber. 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.

If, in addition to the compounds of component A and the compounds of component B, the hair dye additionally comprises hydrogen peroxide or a hydrogen peroxide-containing oxidizing agent mixture, the pH of the hydrogen peroxide-containing hair dye is preferably in a pH range from pH 7 to pH 11, particularly preferably pH 8 to pH 10. The oxidizing agent may be mixed with the hair dye immediately prior to application and the mixture applied to the hair. If the compounds of component A and 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 of component A and the 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 the multilayer molded bodies, the component A is incorporated in one layer and the component B in another layer, wherein between these layers is 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 only immediately prior to use. In dry storage, a defined amount of warm (3O ⁰ C to 8O ⁰ C) water is usually added prior to application and made a homogeneous mixture.

A fourth subject of the invention is the use of at least one compound according to formula (Ia) and / or its tautomer (Ib) as component A,

wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Y, X ^" , Het and X ^{1 are} as defined in the first subject of the invention, for the purpose of nuancing oxidation dyeings of keratin-containing fibers, in particular human hair Whether shading occurs simultaneously during oxidative staining or oxidative staining is timed before shade.

A fifth object of the invention is the use of at least one compound according to formula (Ia) and / or its tautomer (Ib) as component A,

wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Y, X ^" , Het and X ^{1 are} as defined in the first subject of the invention for color refreshment of oxidative coloring dyed keratin-containing fibers.

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 in accordance with the invention to use a combination of at least one compound of component A and at least one compound of component B for such a color refreshment, so that a further subject of the present invention is the use of at least one compound according to formula (Ia) and / or its Tautomer (Ib) as

Component A,

(Ia) (Ib) wherein R ¹ , R ² and R ^{3 are} as defined in the first subject of the invention together with at least one CH-acidic compound of the formulas (II) and / or (IM) as component B

wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Y, X ^' , Het and X ^{1 are} as defined in the first subject of the invention for color refreshment of oxidative coloring dyed keratin-containing fibers.

B e i s p e e l e

S y n t e s e p e s e s e

1.1 Preparation of 2-chloro-3- (hydroxymethylene) cyclohex-1-en-1-carbaldehyde (A1)

37.76 g (0.517 mol) of dry dimethylformamide (DMF) were introduced into a 500 ml flask equipped with stirrer, reflux condenser, internal thermometer and dropping funnel and cooled by means of an ice bath. Subsequently, 60.87 g (0.400 mol) of phosphorus oxychloride were slowly added dropwise over 45 minutes. During the dropping, the temperature was maintained at 10 to 15 ⁰ C. Thereafter, the ice bath was removed and replaced with a water bath, it was further stirred for 30 minutes. To the thus prepared Vilsmeier adduct was added dropwise a solution of 10.00 g (0.102 mol) of cyclohexanone in 50 ml of dry dimethylformamide. After the dropwise addition, the water bath was removed, and the orange reaction solution was heated at 50 to 60 ^° C. for 3 hours.

The orange-red solution was poured cautiously onto 300 ml of ice, 200 ml of distilled water was added, and the resulting mixture was stirred. After about 20 minutes, a yellow solid began to precipitate. It was stirred overnight, the yellow solid was filtered off and washed several times with water until neutral. Subsequently, the solid was dried in a drying oven. Yield = 12.9 g (72.9%) mp = 124-126 ⁰ C.

1.2 Preparation of 2-chloro-3- (hydroxynethylene) -5-methylcyclohex-1-en-1-carbaldehyde (A2)

37.76 g (0.517 mol) of dry dimethylformamide (DMF) were introduced into a 500 ml flask equipped with stirrer, reflux condenser, internal thermometer and dropping funnel and cooled by means of an ice bath. Subsequently, 60.87 g (0.400 mol) of phosphorus oxychloride were slowly added dropwise over 45 minutes. During the dropping, the temperature was maintained at 10 to 15 ⁰ C. Thereafter, the ice bath was removed and replaced with a water bath, it was further stirred for 30 minutes. To the thus prepared Vilsmeier adduct was added dropwise a solution of 11.22 g (0.100 mol) of 4-methylcyclohexanone in 55 ml of dry dimethylformamide. After the dropwise addition, the water bath was removed, and the orange reaction solution was heated at 50 to 60 ^° C. for 3 hours.

The orange-red solution was poured cautiously onto 300 ml of ice, 200 ml of distilled water was added, and the resulting mixture was stirred. After about 20 minutes, a yellow solid began to precipitate. The mixture was stirred overnight, the solid was filtered off and washed several times with water until neutral. Subsequently, the solid was dried in a drying oven. Yield = 13.1 g (70.1%) Melting point = 140 - 142 ⁰ C.

1.3 Preparation of 2-chloro-3- (hydroxymethylene) -6-methylcyclohex-1-en-1-carbaldehyde (A3)

37.76 g (0.517 mol) of dry dimethylformamide (DMF) were introduced into a 500 ml flask equipped with stirrer, reflux condenser, internal thermometer and dropping funnel and cooled by means of an ice bath. Subsequently, 60.87 g (0.400 mol) of phosphorus oxychloride were slowly added dropwise over 45 minutes. During the dropping, the temperature was maintained at 10 to 15 ⁰ C. Thereafter, the ice bath was removed and replaced with a water bath, it was further stirred for 30 minutes. To the thus prepared Vilsmeier adduct was added dropwise a solution of 11.22 g (0.100 mol) of 3-methylcyclohexanone in 55 ml of dry dimethylformamide. To the dropwise addition of the water bath was removed and the orange reaction solution was heated to 50 to 60 ⁰ C for 3 hours.

The orange-red solution was poured cautiously onto 300 ml of ice, 200 ml of distilled water was added, and the resulting mixture was stirred. After about 20 minutes, a yellow solid began to precipitate. It was stirred overnight, the yellow-brown solid was filtered off and washed several times with water until neutral. Subsequently, the solid was dried in a drying oven. Yield = 11, 8 g (63.2%) mp = 135-137 ⁰ C.

For b e b e s p e e l e

1.0 Preparation of a coloring agent:

Aqueous gel formulation for component A gel 2

Inventive aldehyde (component A) 10 mmol Natrosol HR 250 2 g

NaOH (50%, aqueous solution) possibly a few drops of water, fully desalted ad 100 g

Aqueous gel formulation for Component B Gel 1

C, H-acidic compound (component B) 10 mmol Natrosol HR 250 2 g isopropanol 10 g water, fully desalted ad 100 g

The aldehyde according to the invention (component 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.

The C, H-acidic compound (component B) was first dissolved or suspended in a little water with stirring, then made up to 98 g with water. While stirring, the Added Natrosol and waited for the swelling process. 2.0 colorations

The two aqueous gel formulations (Gel 1 and Gel 2) were mixed in a ratio of 1: 1, then, depending on the pH, a pH of 9 was set 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. The result is shown in Table 1.

Table 1: staining results

Al 2-chloro-3- (hydroxymethylene) cyclohex-1-en-1-carbaldehyde

A2 2-Chloro-3- (hydroxymethylene) -5-methylcyclohex-1-en-1-carbaldehyde

A3 2-Chloro-3- (hydroxymethylene) -6-methylcyclohex-1-en-1-carbaldehyde

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

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

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

Claims

Patent claims

1. An agent for dyeing keratin-containing fibers, in particular human hair, containing in a cosmetic carrier

where n is 1 or 2,

R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -alkoxy group, an aryl group, a (C ₁ to C ₆ ) -alkoxy - (d to C ₆ ) alkyl group, wherein in the event that n is 1, the radicals R ¹ and R ³ or R ¹ and R ² or R ² and R ³ , in each case together with the remainder of a five-membered ring, six-membered ring or seven-membered ring, which in turn may be substituted by at least one radical selected from a hydrogen atom, a halogen atom, a (Ci to C ₆ ) alkyl group, a (Ci to C ₆ ) alkoxy group, an aryl group, a (Ci to C ₆ ) - alkoxy (Ci to C ₆ ) -alkylgruppe, together with

At least one CH-acidic compound as component B, selected from at least one compound according to formula (II) and / or formula (IM),

wherein

R ⁶ and R ⁷ are independently a linear or cyclic Ci-C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl Ci-C ₆ - alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a d-Ce-alkoxy-d-Ce-alkyl group, a group R ¹ R ¹¹ N- (CH ₂ ^ -, wherein R ¹ and R ¹¹ independently of one another represent a hydrogen atom, a C 1 -C ₄ -alkyl group, a C 1 -C ₄ -hydroxyalkyl group or an aryl-C ¹ -C ₆ -alkyl group, where R ¹ and R ¹¹ together with the nitrogen atom are a Can form a 5-, 6- or 7-membered ring and m stands for a number 2, 3, 4, 5 or 6,

R ⁸ and R ¹⁰ independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, where at least one of the radicals from R ⁸ and R ¹⁰ denotes a C ₁ -C ₆ -alkyl group,

R ⁹ represents a hydrogen atom, a dC ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a dC ₆ alkoxy group, a C-ι-C ₆ -hydroxyalkoxy group, a group R ^m R ^lv N- (CH ₂ ) _q -, wherein R ^m and R ^ιv independently represent a hydrogen atom, a dC ₆ alkyl group, a dC ₆ -Hydroxyalkylgruppe or an aryl-dC ₆ alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ⁹ together with one of the radicals R ⁸ or R ^{10 can form} a 5- or 6-membered aromatic ring optionally with a halogen atom, a dC ₆ alkyl group , a dC ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a dC ₆ alkoxy group, a C ₁ -C ₆ - hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂₎ _S in which R ^v and R ^vι independently of one another represent a hydrogen atom, a C 1 -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group or an aryl-C 1 -C ₆ -al kylgruppe and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

Y represents an oxygen atom, a sulfur atom or a group NR ^V ", wherein R ^v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ - ₆ alkyl group or arylalkyl group, a dC,

Het is an optionally substituted heteroaromatic and X ¹ is a direct bond or a carbonyl group.

2. Composition according to claim 1, characterized in that in the formula (Ia) or (Ib) n, the number 1 means.

3. Composition according to claim 2, characterized in that the radicals R ¹ and R ³ together with the remainder of the molecule form a five-membered, six-membered or seven-membered ring, which in turn may be substituted by at least one radical selected from a hydrogen atom, a halogen atom, a ( C ₁ to C ₆₎ alkyl group, a (C ₁ to C ₆₎ alkoxy group, an aryl group, a (C ₁ to C ₆₎ alkoxy (d to _C6) alkyl group.

4. Composition according to one of claims 1 to 3, characterized in that the agent contains as compound of the formulas (Ia) or (Ib) at least one compound of formula (la-1) and / or its tautomer (lb-1) .

wherein

R ² , R ⁴ and R ⁵ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -alkoxy group, an aryl group, a (C ₁ to C ₆ ) -alkoxy - (d to C ₆ ) alkyl group and the cycle A is a five-membered, six-membered or seven-membered ring.

5. Composition, according to one of claims 1 to 4, characterized in that the agent as the compound of the formula (Ia) or (Ib) at least one unsaturated, non-aromatic dicarbonyl compound of the formulas (la-2) and / or (lb -2) and / or (la-3) and / or (lb-3)

(la-2) (lb-2)

(la-3) (lb-3) woπn

6. Composition according to one of the preceding claims, characterized in that R ^{2 is} a hydrogen atom, a halogen atom is a (C ₁ to C ₆ ) alkoxy group or a (C ₁ to C ₆ ) - alkyl group.

7. Composition according to one of claims 4 to 6, characterized in that R ⁴ and R ^{5 are} independently a hydrogen atom, a hydroxy group, a (C ₁ to C ₆ ) - alkyl group or a (C ₁ to C ₆ ) -hydroxyalkyl group ,

8. Composition according to one of the preceding claims, characterized in that at least one of the following compounds or their tautomer of the formula (Ia) is contained as component A according to formula (Ib):

2-chloro-3- (hydroxymethylene) cyclohex-1-en-1-carbaldehyde

2-chloro-3- (hydroxymethylene) cyclopent-1-en-1-carbaldehyde

3- (Hydroxymethylene) cyclopent-1-en-1-carbaldehyde ,, CHO

HO '

9. Composition according to one of the preceding claims, characterized in that as component B at least one compound is selected, which is selected from the group which is formed from 1, 2-dihydro-1, 3,4,6-tetramethyl -2-oxo-pyrimidinium, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2 oxo-pyrimidinium, 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-diethyl-4-methyl-2-oxopyrimidinium, 1,2-Dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium, 1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxopyrimidinium, 1 , 2-Dihydro-1,3-diphenyl-4-methyl-2-oxopyrimidinium, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium, 1,2-dihydro -1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium, 1, 2-dihydro -1, 3-d iethyl-4,6-dimethyl-2-thioxopyrimidinium, 1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium, 1, 2-dihydro-1, 3-di ( 2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium, 1, 2-dihydro-1, 3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium, 1, 2-dihydro-1, 3 , 4-trimethyl-2-thioxopyrimidiniums, 1, 2-dihydro-1, 3-diethyl-4-methyl-2-thioxo-pyrimidiniums, 1, 2-dihydro-1, 3-dipropyl-4-methyl-2 -thioxo-pyrimidinium, 1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxopyrimidinium, 1,2-dihydro-1,3-diphenyl-4-methyl-2- thioxo-pyrimidinium, 1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium, 1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium, 2- (2-furoyl) -acetonitrile, 2- (5-Bromo-2-fu royl) -acetone Itri I, 2- (5-Methyl-2-trifluoromethyl-3-fluoro) -acetone Itri I, 3- (2,5-dimethyl-3 -furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetone itri I, 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-dimethyl-3-oyl) -acetonitrile,

2- (1, 2,5-trimethylpyrrol-3-oyl) -acetonitrile,

1 / - / - benzimidazol-2-yl-acetonitrile,

1 / - / - benzothiazol-2-yl-acetonitrile,

2- (pyrid-2-yl) acetone itri I,

2,6-bis (cyanomethyl) pyridine,

2- (Indol-3-oyl) -acetonitrile,

2- (2-methyl-indol-3-oyl) -acetonitrile, δ-cyanoacetyl-T-methoxy-methylcarnarin,

2- (2-isopropyl-5,6-benzoquinoline-4-oyl) -acetonitrile,

2- (2-phenyl-5,6-benzoquinoline-4-oyl) -acetonitrile,

2- (quinoxalin-2-yl) acetonitrile,

2- (Cu-maron-2-yl) acetone itri I,

6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro-1-benzofuran-2-carboxylic acid tert-butyl ester,

2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and

2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) -acetonitrile.

10. Composition according to one of the preceding claims, characterized in that in addition at least one CH-acidic compound is contained as component C, which is selected from at least one compound of the group consisting of physiologically acceptable anions, in particular p-toluenesulfonates, methanesulfonates, Hydrogen sulfates, tetrafluoroborates and halides, such as the chlorides, bromides and iodides, formed salts of 1, 4-dimethylquinolinium, 1-ethyl-4-methyl-quinolinium, 1-ethyl-2-methyl-quinolinium, 1, 2,3,3-tetramethyl 3H-indoliums, 2,3-dimethyl-benzothiazoliums, 2,3-dimethyl-naphtho [1,2-d] thiazoliums, 3-ethyl-2-methyl-naphtho [1,2-d] thiazoliums, 3-ethyl -2-methylbenzoxazoliums, 1, 2,3-trimethylquinoxaluminum, 3-ethyl-2-methylbenzothiazoliums, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidiniums, 1, 2 Dihydro-1, 3,4-trimethyl-2-oxopyrimidinium, 1,2-dihydro-4,6-dimethyl-1,3-dipropyl-2-oxopyrimidinium, 1,2-dihydro-1,3-diene , 4,6-tetramethyl-2-thi oxo-pyrimidinium, 1, 2-dihydro-1, 3,4,5, 6-pentamethyl-2-oxopyrimidinium, 1-allyl-i, 2-dihydro-3,4,6-trimethyl-2-oxo pyrimidiniums, 2,5-dimethyl-3- (2-propenyl) -1, 3,4-thiadiazoliums, 3-ethyl-2,5-dimethyl-1, 3,4-thiadiazoliums, 1, 2

Dimethylquinolinium and 1,3,3-trimethyl-2-methylenindoline (Fischer's base), as well as oxindole, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1, 2-dione, indan-1, 3-dione , indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2- (2-furanoyl) acetonitrile, 2- (2-theonyl) acetonitrile , 4,5-dihydro-4-imino-2- (1-piperidinyl) - thiazole (hydrochloride), 4,5-dihydro-4-imino-2- (4-morpholinyl) thiazole (hydrochloride), 4,5-dihydro-4-imino-2- (1-pyrrolidinyl) thiazole (hydrochloride) ,

11. Composition according to one of the preceding claims, characterized in that additionally at least one reactive carbonyl compound is contained as component D, which is selected from at least one compound of the group consisting of benzaldehyde and its derivatives, cinnamaldehyde and its derivatives, naphthaldehyde and its derivatives , 5- (4-Dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3 , 4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4- Morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 6- (4-

Dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-diene-2 on, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (4-piperidinophenyl ) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2-one , 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4- Formyl 1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1, 2-dimethylpyridinium, 4-formyl-1 , 3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, A-acetyl-1-methylquinolinium , 5-form yl-i-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium , 7-Formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1 benzylchinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6- Acetyl-1-methylquinolinium, 7-acetyl-1-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium , 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1 allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl-1-allyl-quinolinium and 8-acetyl-1-allyl-quinolinium, 9-formyl-10-methylacridine ium, 4- (2'-formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'-formylphenyl) -benzimidazolium, 1, 3-dimethyl-2- (4'-formylphenyl) - imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-Formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-Formyl-2'-thienyl) -3-ethylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolinyl, 2- (4'-formyl-1-naphthyl) -3- methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolinyl, 2- (4'-formylphenyl) -3,5-dinethylbenzothiazolene benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate , sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin , 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfoisatin, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

12. Composition according to one of the preceding claims, characterized in that the compounds of component A, the compounds of component B and optionally the compounds of component C and D 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 included.

13. Composition according to one of the preceding claims, characterized in that it contains color enhancers selected from at least one compound of the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2nd -Hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine or any mixtures thereof contains.

14. Composition according to one of the preceding claims, characterized in that it additionally contains at least one substantive dye, preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant.

15. Composition according to one of the preceding claims, characterized in that it additionally contains anionic, zwitterionic or nonionic surfactants.

16. Use of at least one compound according to component A according to claim 1, in combination with at least one compound of component B according to claim 1, as a coloring component in hair dyes.

17. A process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant, according to any one of claims 1 to 15, and conventional cosmetic ingredients, applied to the keratin fibers, some time, usually about 15-30 minutes, on the fiber leave and then rinsed out or washed out with a shampoo.

18. The method according to claim 17, characterized in that the keratin-containing fibers, before a colorant according to any one of claims 1 to 15 is used, were bleached in the context of a pretreatment with a Blondiermittel or dyed with an oxidation dye.

19. Use of at least one compound of component A according to claim 1 together with at least one CH-acidic compound of component B according to claim 1 for the nuancing of oxidation dyeings of keratin-containing fibers, in particular human hair.

20. Use of at least one compound of component A according to claim 1 together with at least one CH-acidic component of component B according to claim 1 for color refreshment of keratin-containing fibers dyed with oxidative dyes.