WO2006102987A1 - Agents for colouring fibres containing keratin - Google Patents

Abstract

The invention relates to agents for the oxidative colouring of fibres containing keratin, in particular human hair, said agents containing compounds of formula (I) as an oxidation colorant intermediate product, in which the groups R<SUP>1</SUP>, R<SUP>2</SUP>, R<SUP>3</SUP>, X, A and An<SUP>-</SUP> are defined as cited in claim 1. The colorant intermediate products are suitable for atmospheric oxidation colouring or colouring in the presence of additional oxidation agents, such as e.g. hydrogen peroxide. The invention also relates to the use of the derivatives according to formula (I) for colouring fibres containing keratin and to a corresponding method for colouring fibres containing keratin, in particular human hair.

Description

'Imittel for dyeing keratin-containing fibers'

The invention relates to compositions for the oxidative dyeing of keratin-containing fibers, in particular human hair, containing specific cationic, heterocyclic compounds, the use of these compounds for dyeing keratin-containing fibers, and to a corresponding process for dyeing keratin-containing fibers, in particular human hair.

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

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

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4, 5,6-tetraminopyrimidine, 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 and 2,5,6-triamino-4-hydroxypyrimidine.

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

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

With oxidation dyes, intensive colorations with good fastness properties can be achieved. Still problematic is the provision of oxidation hair dyeings with sufficient fastness properties, in particular with very good fastness to light, washing and rubbing.

Furthermore, p-phenylenediamine and its derivatives can be found in some persons, the so-called; Parallergic, cause allergic reactions. It is therefore always an object to provide colorants, in particular for the coloring of keratin-containing fibers such as hair, which do not have an allergenic effect. Consequently, it is desirable to develop oxidative dyes which are not derived from p-phenylenediamine yet possess excellent dyeing properties.

Surprisingly, it has now been found that the compounds according to formula I dye keratin-containing fibers oxidatively and the resulting dyeings have excellent fastness properties. They give colorations with excellent brilliance And ¹ 'color depth and lead to shades in the blue to red range. The oxidative

'

Coupling obtained dyes are also excellent for use in

Hair dyes.

A ', first object of the invention are means for dyeing keratin fibers, in particular human hair, which contain in a cosmetic carrier at least one compound according to formula I,

wobei

in which

R ¹ represents a linear or cyclic C _r C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an Ai ^{^} yI (C ₁ -C ₆ ) alkyl group, a Ci-C ₆ -monohydroxyalkyl group, a 'C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy (C ₁ -C ₆ ) alkyl group, a group R ¹ R ¹¹ N- (CH ₂ ) _m -, wherein R ¹ and R ¹¹ are independently a hydrogen atom, a C _r C ₆ alkyl group, a -C ₆ hydroxyalkyl group, or an aryl (C _{r C6)} - alkyl group, wherein R ¹ and R ¹¹ a together with the nitrogen atom, optionally substituted, 5-, 6- or 7-membered ring, and m is an integer from 2 to 6,

R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ -alkyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ -monohydroxyalkyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -hydroxyalkyl group C ₆ alkoxy, a hydroxy (dC ₆ ) - alkoxy group, a group R ¹¹¹ R ¹ V (CHz) _n -, wherein R ¹ "and R ^IV independently represent a hydrogen atom, a Ci-C ₆ alkyl group , a C ₁ -C ₆ -hydroxyalkyl group or an alkyl-C ₁ -C ₆ -alkyl group and n is an integer from 0 to 6, or together with the residual molecule form an aromatic, optionally substituted six-membered ring, X represents an oxygen atom, a sulfur atom, a methylene group CR ⁴ R ⁵ , a vinylene group -CR ⁶ = CR ⁷ - or a group -NR ^7a - where R ⁴ , R ⁵ , R ⁶ and R ⁷ independently of one another a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ - alkyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ - monohydroxyalkyl, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy group, an hydroxy, alkoxy (C _r C ₆₎ a group R ^v R ^vl N- (CH _{2) m} -, in which R ^V and R ^VI atom independently represent a hydrogen, C-ι-C ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group or an aryl Ci-C ₆ alkyl group and m stands for an integer of 0 to 6, and R ^7a is selected from the residues defined under R ^1,

A is a CR ^7b H group in which R ^{7b is} a hydrogen atom or a (C ₁ -C ₄ ) -alkyl group,

• An ^" stands for a physiologically compatible anion.

The substituent -A-NH _{2 of} the formula I preferably binds at the ortho position to the iminium nitrogen atom of the heterocycle. A bond to the ortho position means, according to the invention, a bond to the CH group directly adjacent to the iminium nitrogen atom of the heterocycle. Particularly preferably, the group -A-NH _{2 is} in conjugation via a double bond system to the iminium nitrogen atom.

Particularly preferably, A in formula (I) is a CH ₂ group.

It is inventively preferred that the substituents R ² and R ³ form an aromatic, optionally substituted six-membered ring (Benzannelierung) together with the remainder of the molecule. This six-membered ring is in turn preferably with two radicals R ⁸ and R ⁹ substituted which are independently atom for a hydrogen atom, a halogen atom, a linear or branched d-Cβ alkyl group, a cyano group, a hydroxy group, a C _r C ₆ monohydroxyalkyl , a C ₂ -C ₆ -

Polyhydroxyalkyl group, a C _r C ₆ alkoxy group, a hydroxy (C _r C ₆ ) alkoxy group, a group R ^vll R ^VIII N- (CH ₂ ) _r -, wherein. R ^v "and R ^vι " independently represent a hydrogen atom, a C-rCe-alkyl group, a Ci-C ₆ -Hydroxyalkylgruppe or an aryl-d-Ce-alkyl group and r is an integer from 0 to 6.

The formula I preferably represents compounds of the formulas II, III, IV, V, VI and VIl,

wherein the radicals R ¹ , R ² , R ³ , R ⁴ , R ^s , R ^7a , R ⁸ , R ⁹ , A, and the anion An ^"are as defined in formula I, or according to their preferred embodiments Formulas VI and VII bind the group -A-NH ₂ preferentially to positions 2 and 4 of the pyridinium or quinolinium heterocycle.

Preferably, the compounds are according to. Formula I selected from salts with counterion An ^' the group consisting of 2-aminomethyl-1,3,3-trimethylindolium, 2- (1-aminoethyl) -1,3,3-trimethylindolinium, 2-aminomethyl-3-methylbenzothiazolium, 2 - Aminomethyl-3-methylbenzoxazolium, 2-aminomethyl-1, 3-dimethyl-benzimidazolinium, 2-aminomethyl-1-methyl-quinolinium and 4-aminomethyl-1-methyl-quinolinium.

If the compounds according to the invention are present as salts, they are preferably formed by reaction of the compounds of the formula I with organic or inorganic acids. The salts are preferably physiologically compatible. The anion An ^' is preferably selected from the group of the anions halide, benzenesulfonate, p- Toluene sulfonate, C _r C ₄ alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, (C ₁ - C ₄ ) alkyl sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate and Tetrachlorozinkat selected.

In the following, examples of the groups or radicals mentioned as substituents in the context of this application will be mentioned. Examples of linear and branched

C 1 -C ₈ -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Examples of corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl.

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

CrC ₆ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group.

The methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-

Butoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl are examples of

C _r C ₄ alkoxycarbonyl groups; the methoxycarbonyl and ethoxycarbonyl groups are particularly preferred.

Furthermore, as preferred examples of a Ci-C6-Mdnohydroxyalkylgruppe a

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

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

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

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

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and the

Methoxyhexylgruppe are examples of inventive C ₁ -C ₆ -Akoxy-C ₁ -C ₆ - alkyl groups.

A preferred hydroxy-d-Ce-alkoxy group is the 2-hydroxyethoxy group.

Preferred aryl groups are phenyl, naphthyl and biphenyl.

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

Preferred arylC _r C ₆ alkyl groups are benzyl and 2-phenylethyl.

The amino, diethylamino, dimethylamino, di (2-hydroxyethyl) amino, (2

Hydroxyethyl) amino, aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-

Dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl, 2-dimethyl-aminoethyl, piperidinomethyl, pyrrolidinomethyl, morpholinomethyl are preferred radicals of the group R'R "N- (CH ₂ ) _π -, with the diethylaminomethyl, piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and amino groups being particularly preferred.

A preferred C _1-4 carboxyalkyl group is the 3-carboxypropyl group. The groups 1-carboxypropylene and 1-carboxyethylene are preferred carboxy (C _r C ₄ ) ^' alkylene groups.

The other terms used are derived according to the invention from the definitions given here.

The compounds according to the invention can be prepared by methods known from the literature, e.g. according to N. Gamon et al., Liebigs Ann. Chem., 1980, 2072-2094.

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 Hydrόxyalkyl- or acetyl cellulose can be used.

When using the dye precursors according to the invention according to formula (I), a dye is already formed under air oxidation. The dye forms under oxidative coupling and ammonia elimination, as exemplified in the following reaction scheme.

The reaction products of the above-described oxidative coupling of the compounds according to formula I are colored and can be used according to the invention as cationic substantive dyes in colorants for keratin-containing fibers. Preferred reaction products as an ingredient of colorants for keratin-containing fibers, in particular human hair, are selected from compounds of the formulas (RP1) to (RP6),

(RP2)

(RP2)

wherein the radicals R ¹ , R ² , R ³ , R ⁴ , A and An ^"are as defined under formula (I) and R ⁸ and R ^{9 are} independently a hydrogen atom, a halogen atom, a linear or branched C _r C ₆ alkyl group, a cyano group, a hydroxy group, a d-Ce monohydroxy acyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a hydroxy (C _r C ₆ ) alkoxy group, a group R ^v "R ^nll N- (CH ₂ ) r, wherein R ^v " and R ^vι "independently of one another represent a hydrogen atom, a Ci-Ce-alkyl group, a Ci-C ₆ -Hydroxyalkylgruppe or an aryl-CrC ₆ - alkyl group and r is an integer of 0 to 6. 10

The reaction products are preferably present in an amount of 0.01-10% by weight, preferably 0.1-3% by weight, based in each case on the ready-to-use colorant.

The reaction products can be used both in the presence of the compounds of formula (I) and in the absence of the compounds of formula (I) in the colorants application. The use of the dye precursors according to formula (I) in the colorants, however, offers advantages in terms of the color fastness of the obtained dyeings. Furthermore, there is the option to use these reactive dye precursors together with other reactants in the compositions of the invention. It may therefore be advantageous to use at least one compound of the formula (I) together with at least one reactive carbonyl compound and / or with at least one oxidation dye precursor of the developer and / or coupler type.

Dyeing with increased brilliance and improved fastness properties (light fastness, wash fastness, rubfastness) over a wide range of nuances are achieved if the compounds of formula I used according to the invention together with at least one substance having a reactive carbonyl group (hereinafter called reactive carbonyl compound) in the inventive compositions are. Reactive carbonyl compounds according to the invention have at least one carbonyl group as reactive group which reacts with the compound of formula I under condensation to form a Schiff base. Furthermore, according to the invention, those compounds which can be used as reactive carbonyl components in which the reactive carbonyl group is derivatized such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the compounds of the formula I are 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) when component B is derived from aldehydes, of water to form hydrates as addition compound to the carbon atom of the carbonyl group of the reactive carbonyl compound, these derivatives are preferably not themselves colored. 11

Preferably, these reactive carbonyl compounds are aldehydes or ketones.

The reactive carbonyl compounds are preferably selected from compounds according to formula VII ₁

in which

• AR is benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1,2,3-triazine, 1, 3,5-triazine, quinoline, isoquinoline, indole, indoline, Indolizine, indan, imidazole, 1,2,4-triazole, 1, 2,3-triazole, tetrazole, benzimidazole, 1, 3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, Acenaphthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenyl ether, azobenzene, chromone, coumarin, diphenylamine, stilbene, wherein the N-heteroaromatics may also be quaternized,

R ^9a represents a hydrogen atom, a C ₁ -C ₆ -alkyl, C ₂ -C ₆ -acyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₄ perfluoroalkyl, an optionally substituted aryl or heteroaryl group .

• R ^10, R ¹¹ and R ¹² independently represent a hydrogen atom, a halogen atom, a C _r C ₆ alkyl, C _r C ₆ alkoxy, Ci-C ₆ aminoalkyl, C ₁ -C ₆ - hydroxyalkyl group, a Ci-Ce-alkoxy-CrCe-alkyloxy, a C ₂ -C ₆ acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, sulfonamide, sulfonamido, C ₂ -C ₆ alkenyl, an aryl, an aryl-C _r C ₆ alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, an amino or ammonio or a 1-imidazol (in) iogruppe, wherein the last three groups having one or more C _r C ₆ alkyl, CRCE-carboxyalkyl, C ₁ -C ₆ - hydroxyalkyl, C ₂ -C ₆ alkenyl, CrCe- alkoxy CRCE alkyl, alkyl with optionally substituted benzyl groups, by sulfo (CrC _4), or heterocycle (C ₁ -C ₄₎ alkyl groups may be substituted, 12 wherein also two of the radicals from R ¹⁰ , R ¹¹ , R ¹² and -ZYR ^9a together with the remainder of the molecule can form a fused-optionally substituted 5-, 6- or 7-ring, which likewise can carry a fused aromatic ring, the system AR being able to carry, depending on the size of the ring, further substituents which, independently of one another, can stand for the same groups as R ¹⁰ , R ¹¹ and R ¹² ,

Z is a direct bond, a carbonyl, a carboxy (C _r C ₄ ) alkylene, an optionally substituted C ₂ -C ₆ alkenylene, C ₄ -C ₆ alkadienylene, furylene, thienylene -, Arylen-, Vinylenarylen-, Vinylenfurfurylen-, Vinylenthienylengruppe, where Z together with the -YR ^9a group can also form an optionally substituted 5-, 6- or 7-ring,

Y is a group which is selected from carbonyl, a group according to formula VIII and a group according to formula IX,

wobei

in which

• R ¹³ represents a hydrogen atom, a hydroxy group, a C ₁ -C ₄ - alkoxy group, a -C ₆ alkyl group, a -C ₆ hydroxyalkyl group, a C ₂ - C ₆ -polyhydroxyalkyl group, a CRCE-alkoxy-alkyl group CRCE .

R ¹⁴ and R ^1S independently of one another represent a C 1 -C 6 -alkyl group, an aryl group or together with the structural element OC-0 of the formula IX form a 5- or 6-membered ring.

The reactive carbonyl compound is more preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4- Hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone,. 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxy acetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4- 13

Aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, Benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, ^^^ trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1 hydroxy-2-

^■ acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9- Ruorenone, 3-hydroxyfluorenone, anthrone, 1, 8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, A-

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-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3, 5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde,. 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-

Trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4- Dihydroxybenzaldehyde, 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-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, A-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, , 2-morpholinobenzaldehyde, A-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2- 14

Hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methpxy-1 - naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, A-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2- Chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) -benzaldehyde, Piperonal, 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-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2 -Methylindol-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ^l, 3 ^l , 3'-trimethyl-2-indolinylidene) -acetoaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, A-acetylpyridine, 2-acetylpyridine, 3 Acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromone-3-aldehyde, 3- (5'-nitro -2'-furyl) -acrolein, 3- (2'-furylj-acrolein and imidazole-2-aldehyde, 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-aceto phenone, 2- (4'-methoxybenzoyl) acetophenone, 2- (2'-furoyl) acetophenone, 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoy!) acetophenone, benzylideneacetone, A-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, A-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylidene acetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-benzylidenecyclohexanone, 2- (4'-hydroxybenzylidene) -cyclohexanone, 2 - (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1,3 cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3 -methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) - cyclopentanone, 2- (4'-dimethylaminobenzylidene) cyclopentanone, 5- (4-dimethylaminophenyl) penta-2,4- 15% of tjenal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-diallyl, 5ir (3,4-dimethoxyphenyl) penta-2,4-dienal, 5 - (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinylphenyl) penta-2,4-dienal, 5- 4-pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-> dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2- Fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro r-3r nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy 5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid , 4-nitro-1-naphthaldehyde, 2-nitromycin aldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl 9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-formyl-1-methylpyridinium, 2-formyl-1 methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, A-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1, 2-dimethylpyridinium, 4-Formyl-1,3-dimethylpyridinium, 4-formyl-1-methyl-quinolinium, 2-formyl-1-methyl-quinolinium, 4-acetyl-1-me ethylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8- Formyl 1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium -, 6-formyl-1-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7 Formyl-allyl-quinolinium and 8-formyl-1-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6-acetyl-1-methyl-quinolinium, 7-acetyl-1-methyl-quinolinium, 8-acetyl-1-methyl-quinolinium, δ Acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 5-acyl 16-tyl-1-benzyl-quinolinylurv, θ-acetyl-benzyl-quinolinium, T-acetyl-benzyl-quinolinium, 8-acetyl-1-benzyl-quinolinium, δ-acetyl-allyl-quinolinium, θ-acetyl-allyl-quinolinium, 7-acetyl-1-allyl-quinolinium and 8-acetyl-i-allylquinolinium, θ-formyl-IO-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'-formylphenyl) benzimidazo. lium, 1,3-pymethyl-2- (4 ¹ -formylphenyl) -imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium , 2- (4'-Formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-fu - ryl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl) 1-naphthyl) -3-methylbenzothiazolium, 6-chloro-1'-formylphenyO-S-methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazolium 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- Nitroisatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carbo-isyatin, 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 and 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 X are preferred,

worin

wherein

R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently hydrogen, halogen, C _r C ₆ alkyl, hydroxy, C ₁ -C ₆ alkoxy, amino, C _r C ₆ dialkylamino , a di (C ₂ -C ₆ -hydroxyalkyl) amino group, a di (C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl) amino group, a C ₁ - 17

G ₆ -hydroxyalkyloxy group, sulfonyl group, carboxyl group, sulfonic acid group, sulfonamido group, sulfonamide group, carbamoyl group, C ₂ -C ₆ acyl group, acetyl group or nitro group,

• _Z 'is a direct bond or a vinyl group,

R ¹⁹ and R ²⁰ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

Very particularly preferred compounds of the reactive carbonyl compounds are selected from the group consisting of vanillin, coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3- dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4- Hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-direthylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde 3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4- 3-ethoxy-4-hydroxy-benzaldehyde 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-di methoxybenzaldehyde, 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, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4- Dihydroxybenzaldehyde, 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-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2- Morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2- 18

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-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2- Chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, and piperonal.

According to the invention, it is desirable to dispense as much as possible with the presence of p-phenylenediamine and its derivatives. However, it is possible to combine the novel oxidation dye precursors of the formula I with conventional developer components and coupler components of the oxidative dyeing.

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

in which

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a d- to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ - AIkOXy- ( 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₎ - 19

: Alkoxy (C ₁ to C ₄ ) alkyl or C ₁ to C ₄ alkyl substituted with a nitrogen containing group;

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

¹ to C ₄ carbamoylaminoalkoxy radical;

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

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-ethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino 2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine , 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-) Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particularly preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are 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 as a developer component 20

Use compounds in the inventive compositions containing at least two aromatic nuclei, which are substituted with 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:

wobei:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt, which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -

Or Y is optionally substituted as 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, of 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 possibly by one or more hydroxyl or C ₁ -

C ₈ alkoxy may be substituted, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -

Polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest or a direct compound for bridging Y ₁

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently

Hydrogen atom, a direct bond to the bridging Y or a C ₁ - to C ₄ -

alkyl, 21 ϊrnt.den the provisos that the compounds of formula (E2) contain only one bridge Y per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred dinuclear developing agents of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, N , N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis ( .beta.-hydroxyethyl) -N, N'-bis (4-aminophenyl) - tetramethylenediamine, N, N'-bis (4-methyl-aminophenyl) tetramethylenediamine, N ₁ N'-diethyl-N, N'-bis - (4-amino-3-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4-aminophenyl) _: 1, 4-diazacycloheptane, N, N ' Bis (2-hydroxy-5-amino-bis-cyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and i, 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, 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 in the compositions according to the invention a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3) 22

wobei:

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a

(C ₁ - to C ₄₎ alkoxy (C _r to C ₄₎ alkyl group a C ₁ - to C ₄ aminoalkyl radical, a

Hydroxy (C _r to C ₄ ) -alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl (C _r to C ₄ ) aminoalkyl or a (di-C ₁ - bis C ₄ alkylamino) -

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

G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- (β, -hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino 2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) -phenol and their physiologically acceptable salts. 23 ^l Very particularly preferred compounds of formula (E3) are p-aminophenol, A- amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, ß-dihydroxyethyl) - and 4- Iphenol amino-2- (diethylaminomethyl) -phenol.

Fehner, 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.

The developer component may preferably be selected from heterocyclic developer components such as the pyridine _^, pyrimidine, pyrazole, pyrazol-Pyrimidiri' 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 24-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.

The optionally additionally contained in the agents according to the invention

Coupler components are preferably selected from m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 , 6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2- Hydroxyethyl) -amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4 dichloro-3-aminophenol,

o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 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 and 1-amino-3-bis (2-hydroxyethyl) - aminobenzene,

o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, Resorcinmonometh ^'yl 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 25

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, ¹ 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, barren

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene,

1-amino-3,4-methylenedioxybenzene and 1- (2-hydroxyethyl) amino-3,4-methylenedioxybenzene.

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

Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, can furthermore be used as precursors of naturally-analogous dyes in the compositions according to the invention. 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.

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

26(Xa)

26

in the independently of each other

- G ²¹ is hydrogen, hydroxy-alkyl group, a C ₁ -C ₄ -AIkYlQrUpPe or a C _r C _4,

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 a C 1 -C ₄ -alkyl group,

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

G ²⁶ is a C ₁ -C ₄ -alkyl radical, and

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

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

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

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

in the independently of each other 27

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

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

G ³² is a C 1 -C ₄ -alkyl group, and

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

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

Worthy of mention in this group are N-methyl-5α-dihydroxy-indole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and in particular the 5,6-dihydroxyindole ,

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, 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 1, Disperse 28

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

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, which is incorporated herein by reference, in claims 6 to 11.

Preferred cationic substantive dyes of group (c) are in particular the following compounds: 29

CH ₃ SO ₄ ^" (DZ1) (Basic Yellow 87)

Cl ^" (DZ2)

(DZ3) (Basic Orange 31)

(DZ3) (Basic Orange 31)

(DZ5) (Basic Red 51) 30

(DZ5) (Basic Red 51) 30

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. 31

G} he inventive compositions according to this embodiment contain the Djrektziehenden dyes preferably in an amount of 0.01 to 20 wt .-%, preferably from 0.01 to 10 wt .-%, each based on the total colorant.

Can continue preparations of the invention in nature vorkom-> me ^'hands dyes, they How-for example, henna red, henna neutral, henna black, chamomile blossom, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, catechu, cedar and Contained in the alcano root.

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

To obtain further and more intense colorations, the compositions according to the invention may additionally contain color enhancers. The color enhancers are preferably selected from 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 agent according to the invention already gives intensive dyeings under air oxidation. It can therefore be dispensed with the presence of additional oxidizing agents. However, it may u. U. be desirable, the inventive compositions to achieve the nuances that are lighter than the keratin-containing fiber to be dyed, hydrogen peroxide or Add 32 other oxidizing agents. Oxidizing agents are generally used in an amount of 0.01 to 6 wt .-%, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ . Mixtures of several oxidizing agents, such as a combination of hydrogen peroxide and peroxodisulfates of the alkali and alkaline earth metals or from iodide ion sources, such as alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates, can be used. 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.

Further possible oxidation catalysts are enzymes especially in the presence of classical developer systems of the p-phenylenediamine or p-aminophenol type. Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.

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

Glucose oxidase and D-glucose,

- glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

Alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or their salts, 33

-pholine oxidase and choline,

^■ amino acid oxidase and amino acids.

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.

The agents according to the invention for the oxidative dyeing of keratinic fibers preferably comprise at least one derivative of the general formula (I) in an amount of from 0.01 to 10% by weight, more preferably from 0.1 to 3% by weight, based on the finished composition Medium. , , , , ; ^■ . , ^{• ■} ;

The agent for coloring keratinous fibers can be selected from any suitable agents that are particularly suitable for dyeing human hair. A cosmetically acceptable carrier used is in particular an otherwise customary carrier of agents for dyeing human hair. Apart from the derivatives of the general formula (I), the colorants according to the invention may be composed according to known colorants or contain the usual ingredients for them.

The compositions of the invention preferably contain the dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic. Carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, Schaumaerqsole 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. 34

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.

A general composition is given below:

Developer, also according to formula (I) 0.05 - 5%

Coupler 0.05 - 5%

Direct dyes, also 0.01-10% reaction products of the oxidative coupling of the compounds according to formula (I)

Surfactants, emulsifiers 0.1 - 20%

Fatty alcohols and other emulsifiers 0.5 - 20%

Complexing agent 0.05 - 10%

Buffering agent 0.1 - 1, 0%

Solubilizer + solvent 0.5 - 15% pH adjuster as needed

Perfume oils 0.1 - 0.6%

Polymers 0.1 - 5%

Water '50 - 98%

Suitable colorant compositions are described, for example, in DE-U1-299 11 819, DE-A-101 25 451, DE-U1-201 11 036, Kosmetik, ed. W. Umbach, 2nd ed. 1995, G. Thieme Verlag Stuttgart , New York.

Examples of further suitable and inventively preferred ingredients, active ingredients, additives and auxiliaries are given below. 35

Vyejterhin. The colorants of the invention may contain all known in such preparations. In many cases, the colorants contain at least one surfactant, whereby in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic iTehsiden.

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 a carboxylate, sulfate, sulfonate or phosphate group un, d is 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 mono-, di- and trialkanolammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (Soaps), ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,

Acylsarcosides having 10 to 18 C atoms in the acyl group, acyl taurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the acyl group Alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 carbon atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms, alpha sulfo fatty acid methyl esters of fatty acids with 12 to 18 C atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12, Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, 36 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 2-15 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.

Nonionic surfactants contain as hydrophilic group z. For example, a polyol group, a polyalkylene glycol ether 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 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and

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

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and 2-methyl-branched aliphatic 37

⁽ s, ch, e radicals) Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, tr-cetyl and 1-stearyl Particular preference is given to 1-octyl, 1-decyl, 1-lauryl, 1 -Myristyl Use of so-called "oxo-alcohols" as starting materials outweighs compounds with an odd number of carbon atoms in the alkyl chain.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds. H

And C ₁₀ alkyl groups, mainly of C ₂ - - and C - ^ - alkyl groups essentially of C ₈ - to Ci6 alkyl groups or Ci essentially of alkyl polyglycosides are those in which R ¹ consists essentially of C ₈ are particularly preferred ₂ - to Ci ₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1.1 to 1.4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired. 38

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

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one -COO ⁹ or -SO ₃ ^("J) group in the molecule. N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name cocamidopropyl betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Under am- pholytischen surfactants are surface-active compounds which, apart from a C ₈ -C ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO ₃ H group and to form internal Salts are capable. 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-cocoalkyl aminopropionate, the Kokosacyiaminoethylaminopropionat and the C _2-18 acyl sarcosine.

According to the invention, the cationic surfactants used may in particular be those of the quaternary ammonium compounds, esterquats and amidoamines type.

Preferred quaternary ammonium compounds are ammonium halides, in particular 39

Yeast chlorides and bromides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylchloronium chloride, as well as the imidazolium compounds known under the INCI names Quatemium-27 and Qüaternium-δS. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

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

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

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

Also useful in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquatemäre polydimethylsiloxanes. 40 quaternium-80).

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

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

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs 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, 41

, zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylamide hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, Vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, ^λ

Thickening agents, such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, e.g. For example, methyl cellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,

Structurants, such as glucose and maleic acid, hair-conditioning compounds, such as PhosRholipide, 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,

Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine, other pH adjusters,

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

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides, 42

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.

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, 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 65 mmol, especially 1 to 40 mmol, based on 100 g of the total colorant.

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

43

lB, e i s p e e I e

On the one hand, dyeings of hair were carried out, during which process the oxidative coupling of the oxidation dye ivoφrodukte of the formula I according to the invention on the hair with the hair dye according to the invention was carried out during the dyeing process. For comparison, the pigments of the oxidative coupling of the oxidation dye precursors of the formula I according to the invention were synthesized and isolated in advance. Subsequently, a dyeing solution with these substantive dye pigments was prepared and dyed on the hair.

1.0 Preparation of a dyeing solution

In each case, a solution of 3 mmol of the compound of the formula I or 1.5 mmol of the reaction product of this compound 30 ml of water at about 50 ⁰ C was prepared. The mixture was adjusted with hydrochloric acid to a pH of pH 4, 6 or 7 (see Table 1). ^■ ...

2.0 colorations

Non-pretreated human hair was inserted into the freshly prepared staining solution at 3O ⁰ C for 30 minutes graying a strand of 90%, is introduced. The tress was then rinsed for 30 seconds with lukewarm water, dried with warm air (30 ⁰ C to 40 ⁰ C) and then combed out.

The respective color shades and color depths of the sample colorations are reproduced in Table 1 below.

Compounds of component A (to Table 1): A1 2-Aminomethyl-1,3,3-trimethyl-3H-indolinium tetrafluoroborate A2 1, 3-bis (1,3,3-trimethyl-2-indolinyl) -2- aza-trimethinium tetrafluoroborate (reaction product of A1 with atmospheric oxygen)

The intensities of the dyeings were evaluated visually according to the following scale:

+++ very strong intensity

++ (+) strong to very strong intensity 44

++ strong intensity

+ (+) medium to high intensity

+ medium intensity

(+) weak intensity no or very pale coloration

Table 1

Claims

There is no such thing Agent for coloring keratin-containing fibers, in particular human hair, containing in a cosmetic carrier at least one compound according to formula I,

where ¹ l • R ¹ represents a linear or cyclic -C ₆ alkyl group, a C ₂ -C ₆ - alkenyl group, an optionally substituted aryl group, an aryl- (dC ₆₎ - alkyl group, a -C ₆ monohydroxyalkyl, a C ₂ -C ₆ Polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy- (C ₁ -C ₆ ) -alkyl group, a group R ¹ R ¹¹ N- (CH ₂ ) _m -, in which R ¹ and R ¹¹ independently of one another represent a hydrogen atom, aCrC ₆ -Alkyl group, a Ci-C ₆ -hydroxyalkyl group or an aryl (C ₁ -C ₆ ) -alkyl group, wherein R ¹ and R "form together with the nitrogen atom, an optionally substituted, 5, 6 or 7-membered ring can, and m stands for an integer from 2 to 6, R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a linear or branched one

a cyano group, a hydroxy group, a Ci-C ₆ monohydroxyalkyl, a C ₂ -C ₆ polyhydroxyalkyl group, a Ci-C ₆ alkoxy group, a hydroxy (CrC ₆₎ - alkoxy group, a group R ¹¹¹ R ¹⁷ N- ( CHa) _n - wherein R ¹ "and R ^IV are independently a hydrogen atom, a Ci-C ₆ alkyl group, a C _r C ₆ hydroxyalkyl group, or an aryl-d- C ₆ alkyl group and n is an integer from 0 to 6, or together with the remainder of the molecule form an aromatic, optionally substituted six-membered ring, X represents an oxygen atom, a sulfur atom, a methylene group CR ⁴ R ⁵ , a vinylene group -CR ⁶ = CR ⁷ - or a group -NR ^7a -, Wherein R ⁴ , R ⁵ , R ⁶ and R ^r independently represent a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ alkyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ monohydroxyalkyl group a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy group, a hydroxy (Ci-C ₆₎ alkoxy group, m- a group R ^v R ^vl N- (CH ₂₎ ^v and where R R ^vι independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an arylCrCe-alkyl group and m is an integer from 0 to 6, and R ^{7a is} from Radicals are defined, which are defined under R ¹ , A is a CHR ^7b group in which R ^{7b is} a hydrogen atom or a (C 1 -C 4) alkyl group, An ^' is a physiologically acceptable anion. 2. A composition according to claim 1, characterized in that it contains at least one compound of formula I, in which the group -A-NH _{2 of} the formula I in the ortho position to the iminium nitrogen atom of the heterocycle binds. 3. Composition according to one of claims 1 or 2, characterized in that in formula IR ² and R ³ together with the remainder of the molecule one with two radicals R ^? and R ⁹ form substituted Benzannelierung, wherein R ⁸ and R ⁹ are independently a hydrogen atom, a halogen atom, a linear or branched C ₁ - C ₆ alkyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ - monohydroxyalkyl , a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a hydroxy (C _r C ₆ ) alkoxy group, a group R ^vll R ^vm N- (CH ₂ ) _r -, wherein R ^v " and R ^vιu independently represent a hydrogen atom, a CrC ₆ alkyl group, a Ci-C ₆ hydroxyalkyl group, or an aryl-C _r C ₆ - alkyl group and R stands for a whole number from 0 to. 6 4. Composition according to one of claims 1 or 2, characterized in that the compounds of formula (I) are selected from at least one of the compounds according to formulas (II), (III), (IV), (V), (VI) and (VII)

wherein R ¹ is a linear or cyclic C _r C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an Ai ^ I (C ₁ -C ₆ ) alkyl group, a Ci-C ₆ - Monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy- rCeJ-alkyl group, a group R ¹ R ¹¹ N- (CH ₂ ) _FH -, wherein R ¹ and R ¹¹ independently represent a hydrogen atom, a C _t -C ₆ alkyl group, a C _r C ₆ hydroxyalkyl group, or an aryl (CrC ₆₎ alkyl group, wherein R ¹ and R ', optionally substituted together with the nitrogen atom form a 5-, 6- or 7-membered And m is an integer of 2 to 6, R ² and R ³ independently represent a hydrogen atom, a halogen atom, a linear or branched C _r C ₆ alkyl group, a cyano group, a hydroxy group, a C _r C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C _r C ₆ alkoxy group, a hydroxy (C _r C ₆ ) alkoxy group , ^" a group R ¹¹¹ R ¹ V (CH ₂ V, wherein R ¹ " and R ^IV independently of one another represent a hydrogen atom, a C _r C ₆ alkyl group, a C _r C ₆ hydroxyalkyl group or an aryl C _r C _6- alkyl group and n is an integer from 0 to 6, 48 or form together with the Restmoleküi an aromatic, optionally substituted six-membered ring, R ⁴ and R ⁵ independently of one another represent a hydrogen atom, a halogen atom, a linear or branched C _r C ₆ -alkyl group, a cyano group, a hydroxy group, a C _r C ₆ -monohydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group , a C _r C ₆ alkoxy group, a hydroxy _(Ci-C6) - alkoxy group, a group R ^v R ^vl N- (CH _{2) m} -, in which R ^v and R ^vl atom independently represent a hydrogen, a C _r C ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group or an aryl-C _r C ₆ alkyl group and m stands for an integer of 0 to 6, R ⁸ and R ⁹ independently of one another represent a hydrogen atom, a halogen atom, a linear or branched C _r C ₆ -alkyl group, a cyano group, a hydroxy group, a C _r C ₆ -monohydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group , a Ci-C ₆ alkoxy group, a hydroxy (Ci-C ₆ ) - alkoxy group, a group R ^vll R ^VIII N- (CH ₂ ) r, wherein R ^ "and R ^vι " independently represent a hydrogen atom , a C _r C ₆ -alkyl group, a C _r C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and r is an integer from 0 to 6, A is a CHR ^7b group in which R ^{7b is} a hydrogen atom or a (C ₁ -C ₄ ) -alkyl group, • An ^" stands for a physiologically compatible anion. 5: Agent according to one of claims 1 to 4, characterized in that A is a CH ₂ group. 6. Composition according to one of claims 1 to 4, characterized in that the compound according to formula (I) is selected from salts with Gegenion An ^' the group consisting of 2-aminomethyl-1,3,3-trimethylindolium, 2- ( 1-aminoethyl) -1,3,3-trimethylcholinium, 2-aminomethyl-3-methylbenzothiazolium, 2-aminomethyl-3-methylbenzoxazolium, 2-aminomethyl-1,3-dimethyl-benzimidazolinium, 2-aminomethyl-1-methyl-quinolinium and 4-aminomethyl-1-methyl-quinolinium. 49 "\ V j:,. .. Λ Composition according to one of claims 1 to 6, characterized in that ange stands for halide, benzenesulfonate, p-toluenesulfonate, dC ₄ alkanesulfonate, Trifluoromethanesulfonate, perchlorate, 0.5 sulfate, (CrC ₄ ) alkyl sulfate, hydrogen sulfate, Tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. 8l 'Composition according to one of claims 1 to 7, characterized in that it color intensifier 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, ryrazole, 1, 2,4-triazole, piperazidine or any mixtures thereof. 9. Composition according to one of claims 1 to 8, characterized in that it additionally contains at least one reactive carbonyl compounds and / or at least one oxidation dye precursor of the developer and / or coupler type. ' 10. Composition according to one of claims 1 to 9, characterized in that it contains at least one substantive dye, preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant. 11. Composition according to one of claims 1 to 10, characterized in that ammonium or metal salts selected from the group of 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. 12. A composition according to any one of claims 1 to 11, characterized, <laß it oxidizing onsmittel, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution contains. 50 13. Composition according to one of claims 1 to 12, characterized in that it contains anionic, cationic, zwitterionic or nonionic surfactants. 14. An agent for coloring keratin fibers, in particular human hair, comprising in a cosmetic carrier at least one reaction product of the oxidative coupling of the compounds according to formula I of claim 1. 15. Use of at least one agent according to any one of claims 1 to 14 for dyeing keratin-containing fibers. 16. A method for dyeing keratin-containing fibers, in particular human hair, wherein a colorant, according to one of claims 1 to 14 applied to the keratin fibers, some time, usually about 15-30 minutes, left on the fiber and then rinsed again or washed out with a shampoo.