WO2006119818A1 - Agents for dyeing keratin-based fibres - Google Patents

Abstract

The invention relates to agents for dyeing keratin-based fibres, in particular human hair, comprising in a cosmetic vehicle, compounds of formula (I) and/or a enol form thereof, wherein not more than two rests R1, R2, R3 and R4 are independently of each other a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulphonamide group, a (C1C6)-alkyl group, a (C1C6)-alkoxy group, a (C2-C6)-alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl-(C1C6)-alkyl group, a (C2-C6)-hydroxyalkyloxy group, a C2-C6)-hydroxyalkyl group, a (C2-C6)-polyhydroxyalkyl or a RIRIIN-(CH2)m group, wherein RI and RII are independently of each other a (C1C6)-alkyl group, a (C2-C6)-alkenyl group or a aryl-(C1C6)-alkyl group, wherein R1 and R11 can form jointly with a hydrogen atom a cyclic 5, 6 or 7-membered compound, m is an 0, 1, 2, 3, 4, 5 or 6 number and X is an oxygen atom, a sulphur atom, or an NR5 group, wherein R5 is a hydrogen atom a (C1C6)-alkyl group, a (C2-C6)-alkenyl group, an aryl-(C1C6)-alkyl group, a (C2-C6)-hydroxyalkyloxy group, an alkoxy (C1C6)-alkyl group or a (C2-C6)-polyhydroxyalkyl group, provided that at least two rests adjacent between R1, R2, R3 and R4 form jointly with a residual molecule an optionally substituted condensed an aromatic, carbocyclic or heterocyclic ring, or an optionally substituted condensed aromatic, carbocyclic or heterocyclic ring combination. The inventive dyeing agents are used for revitalising or nuancing already dyed keratin-based fibres.

Description

"Agent for dyeing keratinous fibers"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, the fused derivatives of benzofuran-3 (2H) -one or of benzothiophene-3 (2H) -one or of 1,2-dihydro-3H- indol-3-ones, the use of these derivatives in agents for dyeing keratin fibers, for color refreshing or nuancing already dyed keratin fibers and a method for dyeing keratin fibers, in particular human hair.

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

The developer components are usually primary aromatic amines having a further free or substituted hydroxy or amino group in 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-tetraminopyrimidin, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 - diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 4,5- Diamino-1- (2-hydroxypropyl) pyrazole. As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used. Suitable coupler substances are in particular α-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3-bis - (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2 -methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

With regard to other customary dye components, reference is expressly made to the series "Dermatoiogy", edited by Ch. Cuinan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, ch. 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 more conditions, but their disadvantage is, _'that the colorations frequently have only inadequate fastness properties. In the patent applications WO-A1 -02 / 22092 and WO-A2-02 / 00180, indigo derivatives without a fused ring are proposed as a component in colorants for keratin-containing fibers.

The patent application WO-A2-00 / 38638 relates to colorants for keratin-containing fibers, which contain, inter alia, benzofuran derivatives in combination with reactive carbonyl compounds. The affected benzofuran derivatives do not carry a fused ring.

Surprisingly, it has been found that dyeings with the fused compounds according to the invention, in particular in combination with reactive carbonyl compounds, give brilliant, bright color shades in the yellow, orange, violet, dark blue and red color range. These dyes have excellent fastness properties, in particular good washing, light, friction, welding and cold wave fastness.

A first subject of the invention is an agent for dyeing keratin-containing fibers, in particular human hair, comprising in a cosmetic carrier at least one compound according to formula I and / or its enol form,

wherein

At most two radicals of R 1, R 2, R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfonamido group, a (C ₁ -C 6 -alkyl group, a (C ₁ -C ₆ ) alkoxy group, a (C ₂ -C ₆₎ alkyl group alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl (CrC _6), a (C ₂ -C ₆₎ -Hydroxyalkyloxygruppe, a (C ₂ - C ₆ ) hydroxyalkyl group, a (C ₂ -C ₆ ) polyhydroxyalkyl group or a Group R ¹ R ¹¹ N- (CH ₂₎ Oi-, wherein R ¹ and R ¹ 'are each independently a (CrC ₆₎ alkyl group, a (C _r C ₆₎ alkenyl group, or an aryl -C ₆ - alkyl group in which R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 0, 1, 2, 3, 4, 5 or 6, and

• X represents an oxygen atom, a sulfur atom or a group NR5 wherein R5 is a hydrogen atom, a (C _{r C6)} alkyl group, a (C ₂ -C ₆₎ alkenyl group, an aryl (C _r C ₆₎ -alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₁ -C ₆ ) -alkoxy (C ₂ -C ₆ ) -alkyl group or a (C ₂ -C ₆ ) -polyhydroxyalkyl group, with the proviso in that at least two adjacent radicals of R 1, R 2, R 3 and R 4 together with the remainder of the molecule form an optionally substituted, aromatic, carbocyclic or heterocyclic fused ring or an optionally substituted, aromatic, carbocyclic or heterocyclic, fused ring system.

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.

Under adjacent residues according to the invention vicinal arranged radicals are defined. That is, at least one combination of R1 and R2, R2 and R3, or R3 and R4 together with the remainder of the molecule form an optionally substituted aromatic, carbocyclic or heterocyclic fused ring or an optionally substituted, aromatic, carbocyclic or heterocyclic fused ring system.

Preferred optionally substituted, aromatic, carbocyclic or heterocyclic fused rings are derived according to the invention from benzene, pyridine, pyrimidine, pyrazole, imidazole, pyrazine, pyrrole, furan, thiophene, isothiazole, thiazole, isoxazole or oxazole, more preferably from the benzene ring. Preferred optionally substituted, aromatic, carbocyclic or heterocyclic fused ring systems are derived according to the invention from naphthalene, quinoline, isoquinoline, benzofuran, benzothiophene, indole, quinoxaline, indazole, indolizine, benzisoxazole, benzoisothiazole, cinnoline, benzoxazole, benzimidazole or benzothiazole.

The rings or ring systems of the invention can be at least one substituent selected from a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxy group, a sulfonamido group, a (CrC ₆₎ alkyl group, a (CrC ₆₎ alkoxy group, a (C ₂ -C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl (C _r C ₆ ) alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyloxy group, a (C ₂ -C ₆ ) - Hydroxyalkyl group, a (C ₂ -C ₆ ) polyhydroxyalkyl group or a group R "'R ^lv N- (CH ₂ ) n- _> wherein R ¹ " and R ^lv independently represent a (C ₁ -C ₆ ) alkyl group , a (C _r C ₆ ) alkenyl group or an aryl-CrC ₆ alkyl group, wherein R ¹ "and R ^ιv together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 0 , 1, 2, 3, 4, 5 or 6, may be substituted.

Compounds of the formula (I) preferably present in the compositions according to the invention are those compounds in which the non-ring-forming radicals of R ₁ , R 2, R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxy group or a C ₁ -C ₆ -alkoxy group, especially preferably for a hydrogen atom, stand.

It is inventively preferred that according to formula (I) exactly two radicals of R1, R2, R3 and R4 with vicinal arrangement to each other, together with the residual molecule form a fused benzene ring. In this case, it is again preferred if the remaining radicals of R 1, R 2, R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxy group or a C 1 -C ₆ -alkoxy group, particularly preferably a hydrogen atom.

Compounds of the formula (I) which are particularly preferred according to the invention are selected from at least one compound of the formulas (II), (III) and / or (IV) and / or their enol forms

wherein

• R6 and R7 independently represents a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxy group, a sulfonamido group, a _(Ci-C6) ~ alkyl group, a stand for a hydrogen atom, (C ₁ -C ₆₎ - alkoxy group, a (C ₂ -C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl (C _r C ₆ ) alkyl group, a (C ₂ -C ₆ ) hydroxyalkyloxy group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ^V R ^VI N- (CH ₂ ) _P -, wherein R ^v and R ^vι independently of one another represent a (C _r C ₆ ) alkyl group , a (C ₁ -C ₆₎ - alkenyl group or an aryl Ci-C ₆ alkyl group, in which R ^V and R ^VI together with the nitrogen atom form a 5-, 6-, or 7-membered ring and p is an Number 0, 1, 2, 3, 4, 5 or 6,

• X represents an oxygen atom, a sulfur atom or a group NR5 group, wherein R5 a hydrogen atom, a (C _{r C6)} alkyl group, a (C ₂ -C ₆₎ alkenyl group, an aryl (CrC ₆₎ - alkyl group, a (C ₂ -C ₆₎ hydroxyalkyl group, a (C ₁ -Ce) -AIkOXy- (C ₂ - C ₆₎ alkyl or a (C ₂ -C ₆₎ polyhydroxyalkyl group.

In this case, it is particularly preferred according to the invention if the radicals R 6 and R 7 are a hydrogen atom.

It is further preferred according to the invention, when in the formulas (I), (II), (III) and (IV) the radical X is an oxygen atom, a sulfur atom or a group NH. An oxygen atom is particularly preferred. Examples of C _r C ₆ -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred

Alkyl radicals.

Examples of (C _{r C6)} alkoxy groups are methoxy, ethoxy and propoxy.

Examples of preferred C ₂ -C ₆ -alkenyl radicals are vinyl, allyl and butenyl.

Preferred optionally substituted aryl groups are phenyl, naphthyl and

Biphenyl.

Preferred aryl (C _r C ₆ ) alkyl groups are benzyl and 2-phenylethyl.

Furthermore, as preferred examples of a C ₂ -C ₆ hydroxyalkyl group, a

Hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a

4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyethyl group. A 2-hydroxyethyl group is particularly preferred.

Examples of a C ₂ -C ₆ acyloxy group are the acetyl group and the propionyl group.

Examples of a C ₂ τC ₆ -polyhydroxyalkyl group are the 2,3-dihydroxypropyl group,

3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

The amino, dimethylamino, diethylamino, methylamino, 2-aminoethyl, 3

Aminopropyl, 2-dimethylaminoethyl, 2-methylaminoethyl, piperidinomethyl,

Pyrrolidinomethyl, and the morpholinomethyl group are examples of a group

R'R "N- (CH ₂ ) _n -, with the piperidinomethyl and the 2-dimethylaminoethyl group being particularly preferred.

With very particular preference the compound according to the invention contains as compounds of the formula (I) at least one of the following compounds (I) and / or their enol form:

The compounds according to formula (I) are CH-acidic compounds. Dyes containing the compounds of formula (I) stain keratin-containing fibers already without the presence of other additives. 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.

The compounds of the formula I are generally known from the literature. They can be prepared by known synthesis processes, for example according to J.L. Adams et al., Journal of Medicinal Chemistry, 1996, 39 (26), 5035-5046.

The compounds according to formula I can be in chemical equilibrium with their corresponding tautomeric enol form (Ia), as illustrated below:

Dyes which contain the compounds of the formula I alone as the coloring component are preferably used for dyeings in the yellow range. Dyeings with still increased brilliance and improved fastness properties (light fastness, wash fastness, rubfastness) over a wide range of shades from yellow to yellowish brown, orange, brown orange, medium brown, dark brown, purple, dark purple to dark greenish brown and black are achieved when the compounds of the formula I used in the invention together with at least one reactive carbonyl compound (referred to below as component B) is contained in the composition according to the invention.

Reactive carbonyl compounds as component B in the context of the invention have at least one carbonyl group as a reactive group which reacts with the CH-acidic compound of formula I 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 B 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 the CH-acidic compounds of the formula I is always present. These derivatives are preferably addition compounds a) of amines and their derivatives 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 B is derived in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred reactive carbonyl compounds of component B are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine 9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1, 3,3- trimethylindoline (Fischer's aldehyde or tribasic aldehyde),

2-indolaidehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2 aldehyde, 4-pyridinealdehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, pyridoxal, antipyrine-4-aldehyde, furfural, 5-nitro- furfural, 2-thenoyl-trifluoro-acetone, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 5 - (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4 - dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 9-methyl-3-carbazolealdehyde, 9-Ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3 carbazolaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-formyl-1-methylpyridinium, 2-formyl-1 -methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyrid inium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1, 3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1 -methylquinolinium, 5-formyl-i-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-i-ethylquinolinium, 6 Formyl-i-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinyl, 6-formyl-1-benzylquinolinium, 7-formyl-i benzyl quinolinium, 8-formyl-i-benzyl quinolinium, 5-formyl-1-allyl quinolinium, 6-formyl-1-allyl quinolinium, 7-formyl-1-allyl quinolinium and 8-formyl-i-allyl quinolinium 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-sulfo-isatin, 5 Carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular having one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl compound in the agents according to the invention. Again, the compounds according to formula (B-1) are preferred,

wherein

R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a C _r C ₆ -alkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, a C ₁ -C ₆ -dialkylamino group, a di (C ₂ -C ₆ - hydroxyalkyl) amino group, a di (C ₁ -C ₆ -alkoxy-CrC ₆ alkyl) aminoguppe, j _{e n} e C ₁ - C ₆ -Hydroxyalkyloxygruppe, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group, an acetyl 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.

The derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component B are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1 naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo 4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2 - methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-

Ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4- Hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6- diethoxy-4- hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2- hydroxy-benzaldehyde, 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-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2, 5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methyl- benzaldehyde, 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-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-

Morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-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, 3-hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5- nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4- Dibutylaminobenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-car boxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4 hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3, 5-diallyl-4-hydroxybenzaldehyde, 3 Allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal.

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 (I) as component A and at least one compound of component B. The compound of component C is selected from CH-acidic compounds other than compounds of formula (I).

The additional CH-acidic compounds of component C are preferably selected from the group consisting of physiologically compatible anions, in particular p-toluenesulfonates, methanesulfonates, hydrogen sulfates,

Tetrafluoroboraten and halides, such as the chlorides, bromides and iodides, formed salts of 1, 4-dimethylchinolinium, 1-ethyl-4-methyl-quinolinium, 1-ethyl-2-methylchinoliniums, 1, 2,3,3-tetramethyl-3H -indoliums, 2,3-dimethylbenzothiazoliums, 2,3-dimethyl-naphtho [1,2-d] thiazoliums, 3-ethyl-2-methyl-naphtho [1,2-d] thiazoliums, 3-ethyl-2 Methyl-benzoxazoliums, 1, 2,3-Trimethylchinoxaliniums, 3-ethyl-2-methyl-benzothiazoliums, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidiniums, 1, 2-dihydro - 1, 3,4-trimethyl-2-oxo-pyrimidiniums, 1, 2-dihydro-4,6-dimethyl-1, 3-dipropyl-2-oxopyrimidiniums, 1, 2-dihydro-1, 3,4 , 6-tetramethyl-2-thioxo-pyrimidiniums, 1, 2-dihydro-1, 3,4,5,6-pentamethyl-2-oxo-pyrimidiniums, 1-allyl-i, 2-dihydro-3,4,6 trimethyl-2-oxopyrimidinium, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium, 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-one methyleneindoline (Fischer's base), as well as oxindole, 3-methyl-1-phenyl-pyrazolin-5-one, indane-1,2-dione, indane-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, 2- (cyanomethyl) benzimidazole, 2- (cyanomethyl) benzothiazole and 2- (2,5-dimethyl-3-yl) furanoyl) acetonitrile. In a third embodiment, the colorant additionally contains at least one reaction product (hereinafter referred to as reaction product RP) of a compound of formula I and a compound of component B as direct dye. Such reaction products RP can z. Example, be obtained by heating the two reactants in an aqueous neutral to slightly alkaline medium, wherein the reaction products RP precipitate either as a solid from the solution or isolated by evaporation of the solution thereof.

For the synthesis of the reaction products RP, molar ratios of component B to the compound according to formula I of about 1: 1 to about 2: 1 may be useful.

The above-mentioned compounds of the formula I, the compounds of the component B, component C and the reaction products RP are each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, used.

In a fourth embodiment, the agents according to the invention may additionally contain at least one developer component and optionally at least one coupler component as oxidation dye precursors.

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 - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to 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 - to C ₄ ) -alkyl radical or a C ₁ - to 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, a C ₂ - bis C ₄ polyhydroxyalkyl, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ - to C ₄ - acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or 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 one another, they may together form a bridging α, ω-alkylenedioxy group, for example an ethylenedioxy group ,

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention 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, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. 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 in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, C ₁ to C ₄ monohydroxyalkylamino groups, Imidazolinium and 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 Fluoropenthenediamine, 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-acet ylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and 5,8-Diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-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 possibly 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 bridge 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-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine ₁ N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) - N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) tetramethylenediamine, N ₁ N'-diethyl-N ₁ N'-bis (4'- amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10- tetraoxadecane and its 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) -methane, 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 ) , alkyl alkoxy (Cr to _C4) a C ₁ - to C ₄ aminoalkyl radical, a hydroxy (C _r to C ₄₎ alkylamino group, a C ₁ - to C ₄ -Hydroxyalkoxyrest, a C ₁ - to C ₄ - hydroxyalkyl (C _r to C ₄₎ aminoalkyl radical or a (di-C ₁ - to C ₄ -alkylamino) - alkyl group (Cr to _C4), and

G ¹⁴ represents 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 - bis C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, a C ₁ to C ₄ -aminoalkyl radical or a C ₁ to C ₄ -cyanoalkyl radical,

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

G ¹⁶ is hydrogen or a halogen atom.

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

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

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

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

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 published patent application 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-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4.5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4 5-diamino-1 - (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3 -methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) -amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) -amino 1-methylpyrazole.

Preferred 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:

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 polyhydroxyalkyl a (C ₁ - to C ₄₎ alkoxy, alkyl (C _r to C ₄₎ a C ₁ - to C ₄ -aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl radical a (C ₁ - to C ₄₎ alkylamino (Cr to _C4) alkyl group a di - aminoalkyl (Cr to _C4), wherein the dialkyl - [(C _r to C ₄₎ alkyl] 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 _r to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a ( C ₁ -, alkyl to C ₄₎ alkylamino (C _r to C ₄₎ a di - [(C _r to C ₄₎ alkyl] - (C ₁ - to C ₄₎ aminoalkyl, wherein the dialkyl residues optionally, a carbocycle 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) aminoalkyl group, an amino group, a C ₁ - to C ₄ -Alkyi- or di (C ₁ - to C ₄ -hydroxyalkyl) -amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0, if p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or

NG ^ia G " ^u ) 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:

In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E4):

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

2,5-dimethyl-pyrazolo [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-ylamino) ethanol;

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

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

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

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

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

The pyrazolo [1, 5-a] pyrimidines of the above formula (E4) can as described in the literature by cyclization from an aminopyrazole or from Hydrazine be prepared.

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, resorcinomonomethylether, 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.

According to preferred coupler components are

- M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyi-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 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-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2- [3-morpholine-4 -ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzo! and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene, Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy 4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

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

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives, such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4 hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1 - (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.

Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

In addition, in a fifth embodiment as precursors of naturally-analogous dyes, such indoles and indolines are preferably used in the compositions according to the invention which contain at least one hydroxyl or Amino group, preferably as a substituent on the six-membered ring, have. 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.

Especially suitable as precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula Va ₁

(Va)

in the independently of each other

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

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

- G ²³ is hydrogen or an alkyl group ₄ C _r C,

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

- G ²⁵ is 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 are within this group N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindo! In, N-butyl-5,6-dihydroxyindoline and in particular the 5,6-Dihydroxyindolin.

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

(Vb)

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, where the -COOH group may also be present as a salt with a physiologically compatible cation,

- G ²⁹ is hydrogen or an alkyl group ₄ C _r C,

G ³⁰ is hydrogen, a C _r C ₄ alkyl group or a group -CO-G ³² , in which G ³² is a C _r 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, the sulfates and hydrobromides, are used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment, it is preferred to formulate the agent according to the invention free of oxidizing agents. On the presence of oxidizing agents, for. B. H ₂ O ₂ , can be omitted in particular 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 likewise 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 ammonium, the alkali or alkaline earth metals, or, for example from iodide ion sources, such as alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates, can be used. 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. Examples of suitable enzymes are peroxidases, which can markedly 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 onto these To activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

Pyranose oxidase and 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 having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as' 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5 -chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-ca hydrobromic 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.

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)

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 ^® are, according to the invention 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 of the invention may also naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkanel.

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, minor amounts may contain other components, as far as they are not Dyeing result adversely affect or 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 the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-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 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the total 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 derivatives of the general formula (I), the colorants according to the invention may be composed in accordance with known colorants or are conventional for these Contain ingredients.

The agents according to the invention preferably contain the compounds of the formula (I) 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 of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.

In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts 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 = O or 1 to 16, acylsarcosides having 10 to 18 C Atoms in the acyl group, acyl taurides having 10 to 18 carbon atoms in the acyl group, acyl isethionates having 10 to 18 carbon atoms in the acyl group,

Sulfobernsteinsäuremono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefinsulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in the R is a preferably linear alkyl group with 10 bis 18 C atoms and x = O or 1 to 12,

Blends of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,

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

Esters of tartaric acid and citric acid with alcohols which are adducts of about 2 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 C 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 at least one quaternary ammonium group and at least one -COO ⁹ or -SO ₃ ^H group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example example, the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylam- moniumglycinate, for example Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline having in each case 8 to 18 carbon atoms in the Alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethyl- glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ . ₁₈ alkyl or acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming 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 each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-co kosalkylaminopropionat, cocoacylaminoethyl aminopropionate and C _12- 18 acyl sarcosine.

Nonionic surfactants contain as hydrophilic group z. B. a polyol group, a polyalkylenglykolethergruppe or a combination of polyol and Polyglykolether- group. Such compounds are, for example

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

Atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,

C _2-22 fatty acid monoesters and diesters of addition products of 1 to 30 mol

Ethylene oxide with glycerine,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,

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

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 methylnosilylamodimethicone), 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 the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", alkyldialkoyloxyalkylammoniummethosulfate such as those sold under the trademark Stepantex ^® methylhydroxy-.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, 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 vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammoniumchlohd / acrylate copolymers and octylacrylamide / methylmethacrylate / tert Butylaminoethylmethacrylat ^ -hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / inyl acrylate copolymers, vinyl acetate tat / 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 arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, eg. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, Clays such as As bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,

Structurants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, for example soya 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,

Antidandruff active ingredients such as Piroctone Olamine and Zinc Omadine, other pH-adjusting agents such as ammonia, monoethanolamine, basic amino acids and citric acid active ingredients 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 alkanolamides,

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. For example, emulsifying greases 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 the ready-to-use colorant.

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

A second aspect of the present invention relates to the use of at least one compound according to formula I and / or its enol form,

wherein R1, R2, R3, R4 and X are defined as described in the first subject of the invention, preferably together with at least one reactive carbonyl compound as component B, as a coloring component in hair dyes.

In a preferred embodiment, those compounds according to formula I are used as coloring component in hair colorants, which consist of those in the first Subject of the invention selected preferred and particularly preferred representatives are selected. The same applies to the compounds of component B.

In addition, it may be preferable to use at least one reaction product RP from a compound according to formula I and a representative of component B as coloring components in hair dyes.

A third aspect of the present invention relates to a process for dyeing keratin-containing fibers; in particular human hair, in which a colorant containing at least one compound according to formula I and / or its enol form,

(I) wherein R1, R2, R3, R4 and X are defined as described in the first subject of the invention, preferably together with at least one reactive carbonyl compound as component B, applied to the keratin-containing fibers, some time, usually about 15-30 minutes on leave 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 input may be provided by an external heat source, e.g. warm air of a hot air blower, as well as, especially when a hair color on living subjects, done by the body temperature of the subject. In the latter case, usually the part to be dyed is covered with a hood.

When the compounds of the formula (I) are used together with the reactive carbonyl compounds of component B, the compounds according to formula I or the compounds of component B, in particular their above-mentioned preferred and particularly preferred representatives, as coloring components either simultaneously on the Hair can be applied or as well successively, ie in a multi-stage process. It does not matter which of the two components is applied first. The optionally contained ammonium or metal salts can be added to the compounds of formula I 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.

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, e.g. a peroxodisulfate 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 comprising the aforementioned oxidation dye precursors as developer and optionally coupler components and optionally mentioned derivatives of indole or indoline is applied to the fiber and after a reaction time optionally with the addition of aforementioned suitable oxidizing agents on the hair for 5-45 minutes the keratin fiber leave. Thereafter, the hair is rinsed. By the subsequent application of the agent according to the invention existing oxidation dyeings can be given a new shade of shade. If the color shade of the agent according to the invention is selected in the same shade of the oxidative dyeing, then the dyeing of existing oxidation dyeings can be refreshed by the process according to the invention. It turns out that the color refreshing or shading according to the method of the invention is superior to color refreshing or shading alone with conventional substantive dyes in the color brilliance and color depth.

Contains the hair dye in addition to the compounds of formula I and optionally the compounds of component B additionally as the oxidizing agent hydrogen peroxide or a hydrogen peroxide-containing oxidant mixture, the pH of the hydrogen peroxide hair dye is preferably in a pH range of pH 7 to pH 11, more 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 the formula I and the component B are applied to the hair in a two-stage process, the oxidizing agent must be used in one of the two process stages together with the corresponding coloring component. For this purpose, it may be preferable to formulate the oxidizing agent with one of the coloring components in a container.

The compounds of formula I 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 multilayered moldings, the component A becomes a layer and the component B a different layer incorporated, between these layers preferably a further layer than

Separating layer is located. The separating layer is free of compounds of components A and

B.

In the separate storage, the reactive components are intimately mixed with each other just before use. When dry storage is before the

Application usually added a defined amount of warm (3O ⁰ C to 8O ⁰ C) water and made a homogeneous mixture.

A fourth subject of the invention is the use of at least one compound according to formula I and / or its enol form,

wherein R1, R2, R3, R4 and X are defined as described in the first subject of the invention, preferably together with at least one reactive carbonyl compound as component B, for the nuancing of oxidation dyeings of keratin-containing fibers, in particular human hair. In use, it is irrelevant whether the shading occurs simultaneously during the oxidative dyeing, or the oxidative dyeing takes place before the shading.

A fifth object of the invention is the use of at least one compound according to formula I and / or its enol form,

(I) wherein R 1, R 2, R 3, R 4 and X are defined as described in the first subject of the invention, preferably together with at least one reactive carbonyl compound as component B for color refreshment of keratin-containing fibers dyed with oxidative colorants.

The dyeings of keratin-containing fibers are known to be exposed to environmental influences, such as light, friction or washes, and may thereby lose brilliance and color depth. In the worst case, if necessary, a nuance shift of the coloring sets in. Such aged dyeings of keratinous fibers, if desired by the user, may be restored to the color state by color refreshment as presented immediately after the initial dyeing. It is according to the invention to use a combination of at least one compound of the formula I _1, preferably in combination with at least one compound of component B, for such a color refreshment.

B e i s p e e l e

Synthesis Example 1 Preparation of naphtho [1,2-b] furan-3 (2H) -one (A1)

To a solution of 80.9 g (0.40 mol) of (1-naphthyloxy) acetic acid in 700 ml of toluene (abs.) Was added dropwise 226.3 g (1.78 mol) of oxalyl chloride, followed by heating at reflux for 30 minutes , After cooling, the reaction mixture was concentrated completely under reduced pressure on a rotary evaporator. 450 ml of toluene (abs.) Were added again, followed by the careful addition of 64.5 g (0.48 mol) of aluminum chloride. The reaction mixture was stirred for one hour at room temperature and then poured onto 1 kg of ice. The solid in the water phase was filtered off and washed with a little water. The toluene phase was washed with saturated sodium chloride solution, the solvent was removed in vacuo on a rotary evaporator. The residue was combined with the previously incurred solid. Yield: 34.2 g (47%) Melting point: 104-113 ⁰ C

¹ H-NMR (400 MHz, DMSO-d6): δ [ppm] = 5.02 (s, 2H); 7.53 (d, 1H); 7.61 (d, 1H); 7.70 (m, 1H); 7.81 (m, 1H); 8.07 (d, 1H); 8.21 (d, 1H)

Synthesis Example 2 Preparation of naphtho [2,1-b] furan-1 (2H) -one (A2)

To a solution of 16.2 g (0.08 mol) of (2-naphthyloxy) acetic acid in 300 ml of toluene (abs.) Was added dropwise 213.3 g (1, 68 mol) of oxalyl chloride, then was for 1, 5 Heated under reflux for hours. After cooling, the reaction mixture was completely concentrated under reduced pressure on a rotary evaporator. 200 ml of toluene (abs.) Were added again, followed by the careful addition of 20.7 g (0.16 mol) of aluminum chloride. The reaction mixture was stirred for 2 hours at room temperature and then poured onto 600 g of ice. The solid in the water phase was filtered off and washed with a little water. Yield: 7.6 g (51%) Melting point: 130-133 ⁰ C.

¹ H-NMR (400 MHz, DMSO-d6): δ [ppm] = 4.94 (s, 2H); 7.48 (d, 1H); 7.53 (m, 1H); 7.73 (m, 1H); 8.03 (d, 1H); 8.32 (d, 1H); 8.61 (d, 1H)

For b e b e s p e e l e

First, the following compositions were prepared:

An aqueous gel formulation for component A (gel 1 J. ^¬

Compound of the formula (I) (component A) 10 mmol Natrosol HR 250 2.5 g isopropanol 10 g water, fully desalted ad 100 g

The compound of formula 1 (component A) was first dissolved or suspended with stirring in a little water and the isopropanol, then made up to 97.5 g with water. While stirring, the Natrosol was added and the swelling process was awaited.

Aqueous gel formulation for Component B (Gel 2):

reactive carbonyl compound (component B) 10 mmol

Natrosol HR 250 2 g

NaOH (50%, aqueous solution) possibly a few drops

Water, demineralized ad 100 g The aromatic aldehyde (component B) 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.

If component A was used together with component B, both aqueous gel formulations (gel 1 and gel 2) were mixed in a ratio of 1: 1 before application. Then the pH was adjusted with ammonia or tartaric acid.

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

A1 naphtho [1,2-b] furan-3 (2H) -one (A1) A2 naphtho [2,1-b] furan-1 (2H) -one (A2)

Component B (to Table 1)

B1 4-hydroxy-3-methoxybenzaldehyde (vanillin)

B2 3-ethoxy-4-hydroxybenzaldehyde (ethyl vanillin)

B3 3,5-dimethoxy-4-hydroxybenzaldehyde

B4 4-hydroxy-2-methoxybenzaldehyde

B5 3,4-Dihydroxybenzaldehyde

B6 3,5-dimethyl-4-hydroxybenzaldehyde

B7 4-hydroxy-3-methylbenzaldehyde

B8 5-Formylsalicylic acid (3-carboxy-4-hydroxybenzaldehyde) Table 1:

Claims

Patent claims

1. An agent for dyeing keratin-containing fibers, in particular human hair, comprising in a cosmetic carrier at least one compound according to formula I and / or its enol form,

wherein

At most two radicals of _R 1, R 2, R 3 and _{R 4} independently of one another represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfonamido group, a (C 1 -C ₆ ) -alkyl group, a (C _r C ₆ ) alkoxy, (C ₂ -C ₆ ) alkenyl, optionally substituted aryl, optionally substituted heterocycle, aryl (C _r C ₆ ) alkyl, (C ₂ -C ₆ ) hydroxyalkyloxy , a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ¹ R ¹¹ N- (CH ₂ ) _H i-. , alkyl group wherein R ¹ and R ¹¹ together with the nitrogen atom form a 5-, - wherein R ¹ and R ¹¹ are independently a (CrC ₆₎ alkyl group, a (C _r C ₆₎ alkenyl group, or an aryl-CrC ₆ Can form a 6- or 7-membered ring and m is a number 0, 1, 2, 3, 4, 5 or 6, and

• X represents an oxygen atom, a sulfur atom or a group NR5, wherein R5 is a hydrogen atom, a (CrC ₆₎ alkyl group, a (C ₂ -C ₆₎ alkenyl group, an aryl (C _{r C6)} alkyl , ₍₆ CRC) a (C ₂ -C ₆₎ hydroxyalkyl group, a - alkoxy (C ₂ -C ₆₎ alkyl group or a (C ₂ -C ₆₎ -polyhydroxyalkyl group, with the proviso that at least two adjacent Radicals of R1, R2, R3 and R4, together with the remainder of the molecule form an optionally substituted, aromatic, carbocyclic or heterocyclic, fused ring or an optionally substituted, aromatic, carbocyclic or heterocyclic, fused ring system.

2. Composition according to claim 1, characterized in that the non-ring-forming radicals of R _1, R 2, R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxy group or a C ₁ -C ₆ -alkoxy group

3. Composition according to one of claims 1 or 2, characterized in that the optionally substituted, aromatic, carbocyclic or heterocyclic fused rings of benzene, pyridine, pyrimidine, pyrazole, imidazole, pyrazine, pyrrole, furan, thiophene, isothiazole, thiazole, Derive isoxazole or oxazole.

4. Composition according to one of claims 1 to 3, characterized in that the optionally substituted, aromatic, carbocyclic or heterocyclic fused ring systems according to the invention of naphthalene, quinoline, isoquinoline, benzofuran, benzothiophene, indole, quinoxaline, indazole, indolizine, benzisoxazole, benzoisothiazole , Cinnoline, benzoxazole, benzimidazole or benzothiazole.

5. Composition according to one of claims 1 to 4, characterized in that the compounds of formula (I) are selected from at least one compound of formulas (II), (III) and / or (IV) and / or their enol forms

wherein

• R6 and R7 independently represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxy group, a sulfonamido group, a (C _r C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkoxy group , a (C ₂ -C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, a Aryl (CrC ₆₎ alkyl group, a (C ₂ -C ₆₎ -Hyclroxyalkyloxygruppe, a (C ₂ -C ₆₎ - hydroxyalkyl group, a (C ₂ -C ₆₎ polyhydroxyalkyl group or a group R "'R ^lv N - (CH _{2) n} - wherein R ¹ "and R ^ιv independently a (d- C ₆₎ alkyl group, a (C _{r C6)} -Alkenyigruppe or an aryl -C ₆ alkyl group, wherein R ¹ "and R ^ιv together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 0, 1, 2, 3, 4, 5 or 6, • X is an oxygen atom, a sulfur atom or a group NR5 group, wherein R5 a hydrogen atom, a (C _{r C6)} alkyl group, a (C ₂ -C ₆₎ alkenyl group, an aryl (C _{r C6)} alkyl group, a (C ₂ - C ₆ ) hydroxyalkyl group, (C ₁ -C ₆ ) alkoxy (C ₂ -C ₆ ) alkyl group or (C ₂ -C ₆ ) polyhydroxyalkyl group.

6. Composition according to one of claims 1 to 5, characterized in that the compounds of formula (I) are selected from at least one compound according to the following group and / or their enol form:

Naphtho [1, 2-ό] furan-3 (2H) -one, naphtho [2, 1-ό] furan-1 (2H) -one, naphtho [2,3-6] furan-3 (2 / - / ) -one, naphtho [1,2-b] thiophene-3 (2H) -one, naphtho [2, 1 -b] thiophene-1 (2H) -one, naphtho [2,3-b] thiophene-3 ( 2H) -one, 1, 2-dihydro-3 / - / - benzo [g] indol-3-one, 2,3-dihydro-1 / - / - benzo [e] indol-1-one, 1, 2 dihydro-3H-benzo [f] indol-3-one.

7. Composition according to one of claims 1 to 6, characterized in that it additionally contains at least one reactive carbonyl compound as component B.

8. Composition according to claim 7, characterized in that the compounds of component B is selected from compounds of formula (B-1),

wherein

R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a C _r C ₆ -alkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, a C ₁ -C ₆ -dialkylamino group, a di (C ₂ -C ₆ - hydroxyalkyl) amino group, a di (Ci-C ₆ alkoxy-C ₆ alkyl) aminoguppe, a C _r C ₆ -Hydroxyaikyloxygruppe, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group, an acetyl 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.

9. Composition according to one of claims 7 or 8, characterized in that the compounds of component B are selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4th -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- 4-hydroxyethylhydroxybenzaldehyde 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxybenzaldehyde 2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl benzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxybenzaldehyde 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, A-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methyl-benzaldehyde, 2,4-dihydroxy-3-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 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-methyl- benzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6- Trihydroxybenzaldehyde, 2,4,5-

Trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro- 4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4- hydroxy-5-methoxybenzaldehyde, A-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1 naphthaldehyde, A-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3, 4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo- 3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4 dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, A- Diethylamino-cinnamic aldehyde, 4-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3 Allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4 hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal.

10. Composition according to one of claims 1 to 9, characterized in that in addition at least one further CH-acidic compound is present as component C, which is different from the compounds of formula (I).

11. A composition according to claim 10, characterized in that the CH-acidic compounds of component C are selected from the group consisting of salts formed with physiologically acceptable anions of 1, 4-dimethylquinolinium, 1-ethyl-4-methyl-quinolinium , 1-ethyl-2-methylquinolinium, 1, 2,3,3-tetramethyl-3H-indolium, 2,3-dimethyl-benzothiazolium, 2,3-dimethyl-naphtho [1,2-d] thiazolium, 3-ethyl 2-methyl-naphtho [1,2-d] thiazolium, 3-ethyl-2-methylbenzoxazolium, 1,2,3-trimethylquinoxaluminum, 3-ethyl-2-methylbenzothiazolium, 1,2-dihydro-1 , 3,4,6-tetramethyl-2-oxo-pyrimidinium, 1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidiniums, 1, 2-dihydro-4,6-dimethyl-1,3 -dipropyl-2-oxopyrimidinium, 1,2-dihydro-1, 3,4,6-tetramethyl-2-thioxopyrimidinium, 1,2-dihydro-1,3,4,5,6-pentamethyl-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-oxopyrimidinium, .2,5-dimethyl-3- (2-prop enyl) -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) , 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, 2- (cyanomethyl) benzimidazole, 2- (cyanomethyl) benzothiazole and 2- (2,5-dimethyl-3-furanoyl) acetonitrile.

12. Composition according to one of claims 1 to 11, characterized in that the compounds of the formula I 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 claims 1 to 12, characterized in that the compounds of component B 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.

14. Composition according to one of claims 10 to 13, characterized in that the compounds of component C 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 included.

15. Composition according to one of claims 1 to 14, characterized in that it color amplifier selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3rd Hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-thazole, piperazidine or any mixtures thereof.

16. Composition according to one of claims 1 to 15, characterized in that it additionally contains oxidizing agent, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution.

17. Composition according to one of claims 1 to 16, characterized in that it additionally contains as oxidation dye precursor at least one developer component and optionally at least one coupler component.

18. Composition according to one of claims 1 to 17, 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.

19. Composition according to one of claims 1 to 18, characterized in that it additionally contains anionic, zwitterionic or nonionic surfactants.

20. Use of at least one compound according to forms! I according to claim 1 as a coloring component in hair dyes.

21. A method for dyeing nucleated fibers, in particular human hair, wherein a colorant, according to any one of claims 1 to 19, 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.

22. The method according to claim 17, characterized in that applied in a two-step process, the component B according to claim 7 before or after application of the compound of formula I according to claim 1 to the keratin fibers, the mixture obtained on the hair for some time, usually about 15-30 minutes, left on the fiber and then rinsed again or washed out with a shampoo.

23. The method according to any one of claims 17 or 18, characterized in that the keratin-containing fibers before a colorant according to any one of claims 1 to 19 is used, were bleached in the context of a pretreatment with a Blondiermittel or dyed with an oxidation dye.

24. Use of at least one compound according to formula I according to claim 1 for the nuancing of oxidation dyeings of keratin-containing fibers, in particular human hair.

25. Use of at least one compound according to formula I according to claim 1 for color refreshment of keratin-containing fibers dyed with oxidative colorants.