WO2006087019A1 - Agents for colouring keratin containing fibres - Google Patents

Abstract

The invention relates to agents for colouring keratin-containing fibres, in particular human hears, comprising in a cosmetically acceptable support at least one type of 1,3-dihydroaza-2H-indole-2-one derivative of formula (I) and/or the physiologically compatible salts thereof, wherein only one of R1, R2, R3 or R4 groups represents N. The use of corresponding agents for colouring keratin-containing fibres and a method for colouring said keratin-containing fibres by applying said agent to the fibres to be coloured are also disclosed.

Description

"Agent for dyeing keratinous fibers"

The present invention relates to agents for coloring keratinic fibers containing specific 1,3-dihydroazaindol-2-ones and to a method of dyeing hair using these agents.

For the dyeing of keratin fibers, in particular human hair, the so-called oxidation colorants play a preferential role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.

Good oxidation dye precursors are primarily intended to meet the following requirements: They must form the desired color shades in sufficient intensity and authenticity in the oxidative coupling. You must also have a good Aufziehvermögen on the fiber, especially in human hair no significant differences between strained and freshly regrowed hair may exist (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids. Finally, if applied as a hair dye, they should not stain the scalp too much and above all they should be safe in terms of toxicology and dermatology. Furthermore, the coloring obtained by bleaching should be easily removed from the hair, if it does not meet the individual wishes of each person and should be reversed,

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

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.

For this reason, alternative dyeing systems have been developed which are based on the reaction of carbonyl compounds with primary amines to a Schiff base or with compounds bearing an acidic hydrogen atom in an aldol condensation.

Also in this dyeing system, a color shade naturally acting on the hair is usually obtained only when various carbonyl components are reacted with various primary amines and / or compounds bearing an acidic hydrogen atom.

Therefore, both the oxidative dyes and the alternative dyeing systems are constantly in need of new, improved dye components which are also unproblematic in terms of toxicology and dermatology.

Colorants containing 1, 3-dihydroaza-2H-indol-2-one derivatives and their use for dyeing nucleated fibers or color refreshing or shading already colored keratin fibers are not yet known.

RW Daisley and JR Hanibali in Synthetic Communications (1981), 11 (9), pp. 743-749 describe the synthesis of A- and 6-azaindol-2 (3H) ones. However, there is no indication of the use of these compounds in Mittein for dyeing keratinous fibers. From A. Marfat, MP. Carta, Tetrahedron Letters (1987), 28 (35), pp. 4027-4030 discloses the preparation of 7-azaoxindoles. Also in this document, a use of such compounds in hair dyes is not mentioned.

The object of the present invention was therefore to develop new dyeing components which meet both the requirements imposed on oxidation dye precursors, in particular with regard to the toxicological and dermatological properties, and allow dyeings in a broad color spectrum with good fastness properties, and thus can be used as coupler component for oxidation dyes , as well as allow use in alternative dyeing systems, the addition of oxidizing agents such. B. H ₂ O ₂ not necessarily require. When used in alternative colorants they should be at least equivalent in terms of color depth and fastness properties, such as light, rubbing and washing fastness and welding and cold wave fastness, the usual oxidation hair colorants. In addition, the colorant must have no or only a very low sensitizing potential.

Surprisingly, it has now been found that specific 1,3-dihydroaza-2H-indol-2-one derivatives satisfy the stated requirements to a high degree and can therefore be used both as a coupler component and as a CH-acidic compound in hair dyes.

A first subject of the present invention are therefore agents for dyeing keratinic fibers, in particular human hair, containing in a cosmetically acceptable carrier at least one 1, 3-dihydroaza-2H-indol-2-one derivative of the formula (I) and / or their physiologically acceptable salts,

in which R ¹ is N or CR ⁶ , R ² is N or CR ⁷ ,

R ³ is N or CR ⁸ ,

R ⁴ is N or CR ⁹ , with the proviso that exactly one of the groups R ¹ , R ² , R ³ or R ^{4 is} N,

R ⁵ is hydrogen, a branched or unbranched linear or cyclic C ₁ to Ce alkyl group, a C ₁ to C ₆ monohydroxyalkyl group, a C ₂ to C ₆ dihydroxyalkyl group, a C _{2 to} C ₆ Alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an arylC _r C ₆ alkyl group, a Ci-Ce-alkoxy-Ci-Cβ-alkyl group, a group R ¹ R ¹¹ N- (CHz) ₁ T ₁ -, wherein R ¹ and R ^{11 are} independently a hydrogen atom, a C _r C ₄ alkyl group, a Ci-C ₄ - hydroxyalkyl group or an aryl-C _r C ₆ alkyl group, wherein R ¹ and R "together with the Nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and

R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, halogen, hydroxy, nitro, carboxy, branched or unbranched linear or cyclic C ₁ to C ₆ alkyl, C ₁ - to C ₆ -mono-hydroxyalkyl group, a C ₂ - to C ₆ -dihydroxyalkyl group, a C ₂ -C ₆ -alkenyl group, a branched or unbranched C ₁ - to C ₆ -alkoxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-Cd-alkyl 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 independently represent a hydrogen atom , a C ₁ -C ₄ -alkyl group, a C _r C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, wherein R ¹ and R ¹¹ together with the nitrogen atom form a 5-, 6- or 7-membered ring can and m stands for a number 2, 3, 4, 5 or 6.

According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the oxidation dyes according to the invention are primarily suitable for dyeing keratin fibers, in principle, there is nothing to prevent their use in other fields, in particular in color photography.

The 1,3-dihydroaza-2H-.indol-2-one derivatives used according to the invention can be converted in the usual way into the known acid addition salts. All statements of this Scripture and accordingly the scope claimed are therefore based on both the present in free form compounds and their water-soluble, physiologically acceptable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.

The keratin fiber coloring agents of the present invention preferably contain at least one 1,3-dihydroaza-2H-indol-2-one derivative of the formula (I) wherein R ^{5 is} hydrogen, methyl or ethyl.

Furthermore, preference is given to those 1,3-dihydroaza-2H-indol-2-one derivatives of the formula (I) in which R ¹ or R ^{4 is} nitrogen and / or the radicals R ⁶ , R ⁷ , R ⁸ present in each case and R ^{9 is} hydrogen.

The 1, 3-dihydroaza-2H-indol-2-one derivatives which are present are therefore particularly preferably 1, 3-dihydro-4-aza-2H-indol-2-one and / or 1, 3 Dihydro-7-aza-2H-indol-2-one.

The hair colorants of the invention contain the 1, 3-dihydroaza-2H-indol-2-one derivative preferably in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total colorant ,

In the following, examples of the groups or radicals mentioned as substituents in the context of this application will be mentioned. Examples of halogen are fluorine, chlorine and bromine, with chlorine being 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 corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl. Examples of preferred C ₂ -C ₆ alkenyl radicals are vinyl and allyl. C 1 -C 6 -alkoxy radicals which are 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 groups are examples of C ₁ -C ₄ alkoxycarbonyl groups; the methoxycarbonyl and ethoxycarbonyl groups are particularly preferred. Furthermore, as preferred examples of a C ₁ -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. The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and the methoxyhexyl group are examples of the present invention Ci-C ₆ -alkoxy-C ₁ -C ₆ - alkyl groups. Examples of a C ₂ -C ₆ -dihydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group. A preferred hydroxyC _r C ₆ 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 atoms being particularly preferred. Preferred C _r C ₆ aminoalkyl groups are the aminomethyl, aminoethyl and aminopropyl groups. Preferred aryl-C-ι-C ₆ alkyl groups are benzyl and 2-phenylethyl. The aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl, dimethylamino, piperidinomethyl, pyrrolidinomethyl, morpholinomethyl and amino groups are examples of a group R'R "N- (CH ₂ ) _m -, with the diethylaminomethyl, piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and amino groups being particularly preferred Examples of a heteroaryl group are pyrrolidyl, 2-furyl, 2-thienyl, 4-pyridyl, 3-pyridyl, 2-pyridyl, triazolyl and 1-imidazolyl. Examples for a heterocycle-C _M alkyl group are pyrrolidino (Ci _-4) alkyl, piperidino (C _1-4) alkyl, morpholino (C _1-4) alkyl, _1-4) alkyl 2-furyl (C, 2-thienyl (C _1-4 alkyl), 4-pyridyl (C. _{1 4} alkyl), 3- pyridyl (C _1-4 ) alkyl, 2-pyridyl (C _1-4 ) alkyl, triazolyl (C _1-4 ) alkyl and 1-imidazoli- (C _1-4 ) alkyl.) A preferred C _{1 4-} carboxyalkyl group is the 3-carboxypropyl group, particularly preferred are C ₂ -C ₆ -alkenylene groups Vinyls and propylene. A particularly preferred C ₄ -C ₆ -alkadienylene group is the 1, 3-butadiene-1, 4-diyl group. Groups 1-Carboxypropylen and 1-carboxyethylene preferred are carboxy (C _r C ₄₎ - alkylene groups. The other terms used are derived according to the invention from the definitions given here.

The 1, 3-dihydroaza-2H-indol-2-one derivatives of the formula (I) can be prepared by conventional organic methods. Particular mention should be made here of the comments by RW Daisley and JR Hanibali in Synthetic Communications (1981), 11 (9), pp. 743-749 and A. Marfat, MP Carta, Tetrahedron Letters (1987), 28 (35 ), Pp. 4027-4030. In a first embodiment of the invention, the 1, 3-dihydroaza-2H-indol-2-one derivative has the function of a coupler component. In this embodiment, the agent according to the invention also contains at least one developer component.

As developer components are usually primary aromatic amines with another, located in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically tolerable salts. 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 C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (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 -Monohydroxyalkylrest, a C ₂ - to 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 form.

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

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

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

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalky! Rest or a direct connection to the bridge Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridging Y per molecule and the compounds of the 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 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, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis N, N'-bis (4-methylaminophenyl ⁾ tetramethylenediamine, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propane-2 -ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

Particularly preferred double bases of formula (E2) are N ₁ N'-bis (.beta.-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-tetraoxadecan or one of its physiologically acceptable salts.

Bis (2-hydroxy-5-aminophenyl) methane is a most preferred dinuclear developing agent of formula (E2). Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

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

G ¹⁴ is a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - Alkoxy (C _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 -mono-hydroxyalkyl 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-hydroxy-methylamino-4-aminophenol , 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol , 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4 -Amino-2- (diethyl-aminomethyl) phenol and their physiologically acceptable salts.

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 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-methoxy-ethyl) -amino-3-amino-6-methoxypyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Laid-Open Patent Publication JP 02019576 A2 or in the 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-di- amino-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 - (ß-hydroxyethyl) amino-1-methylpyrazole.

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

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ Polyhydroxyalkylrest a (C ₁ - to C ₄ J-AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, which may be protected by an acetyl-ureide or a sulfonyl radical can, a (C ₁ - to C ₄₎ alkylamino (C _r to C ₄₎ alkyl group a di - aminoalkyl (C _r to C _4), - [(C _r to C ₄₎ alkyl] the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C _r to C ₄ ) -Amininoalkylrest, the X radicals 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 radical , a C ₁ to C ₄ aminoalkyl radical s alkyl (C _r to C ^ alkylamino ^ r ₄ to C), a di - aminoalkyl group, wherein the dialkyl residues optionally [(C _r to C ₄₎ alkyl] - - (C ₄ to C ₁₎ form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ - hydroxyalkyl) -aminoalkyl radical, an amino radical, a C ₁ - to C ₄ - Alkyl or di- (C ₁ -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 ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

When the pyrazole [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 shown, for example, in the following scheme:

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

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

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

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

2,7-dimethyl-pyrazolo [1,5-aj-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-aminopyrazbl- [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 be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.

Particularly preferred in the inventive compositions in addition to a 1, 3-dihydro-aza-2H-indol-2-one derivative of the formula (I) as a developer component diaminopyrazole derivative, in particular 4,5-diamino-1- (2- hydroxyethyl) pyrazole used.

It is also possible that the keratinic fiber coloring agent of the invention further contains at least one coupler component other than the 1,3-dihydroaza-2H-indol-2-one derivatives of the formula (I).

As further coupler components, for example, m-phenylenediamine derivatives, naphthols, resorcin and resorcinol derivatives, pyrazolones and m-aminophenol derivatives can be used. 1-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl- are particularly suitable as further coupler substances. 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1, 3-bis (2 ', 4 ^l -diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2- Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methyl resorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-amino-phenoxyethanol. 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 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1 -methylbenzol,

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-diaminopyhdin, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3- dihydroxynaphthalene,

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

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxy-pyrimidine, 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. Particularly preferred further coupler components 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, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3 - [( 2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3- [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyi} amino) ethanol, 2 - ({ 3 - [(2-Hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol.

The hair colorants of the invention contain both the developer components and the coupler components preferably in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total oxidation colorant. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proved to be expedient, a certain excess of individual oxidation dye precursors is not detrimental, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1 : 2, may be included.

In a second embodiment of the invention, the 1,3-dihydroaza-2H-indol-2-one derivative functions as a CH-acidic compound. As CH-acidic compounds are generally considered those compounds which carry a hydrogen atom bonded to an aliphatic carbon atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected. In this embodiment, the agent according to the invention furthermore contains at least one reactive carbonyl compound.

Reactive carbonyl compounds according to the invention have at least one carbonyl group as a reactive group which reacts with the CH-acidic compound of the formula (I) to form a carbon-carbon bond. Preferred reactive carbonyl compounds are aldehydes and ketones, especially aromatic aldehydes. Furthermore, according to the invention, those reactive carbonyl compounds in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the CH-acidic compounds of the formula (I) is always present are also usable. 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 (The reactive carbonyl compound 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 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-carb oxaldehyde, 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-methyl-indole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2 -indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, pyridoxal, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl trifluoro-acetone, chromone 3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde, 5- (4-dimethylamino-phenyl) -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-carbazolaldehyde, 9- Ethyl 3-carbazolaldehyde, 3-acetylcarbazole, S.Θ-diacetyl---ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1, 4,9-thmethyl-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, A-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium , 4-formyl-1,3-dimethyl-pyridinium, 4-formyl-1-methyl-quinolinium, 2-formyl-1-methyl-quinolinium, 5-formyl-1-methyl-quinolinium, 6-formyl-1-methyl-quinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-m ethylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl i-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl quinolinium, 5-formyl-i-allyl quinolinium, 6-formyl-i-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 (Ca-1) are preferred,

wherein

• R ^1, R ² and R ³ are independently a hydrogen atom, a halogen atom, a CrCβ alkyl group, a hydroxy group, a C ₁ -C ₆ group -AIkOXy-, a C _r C ₆ dialkylamino group, a di (C C ₂ -C ₆ hydroxyalkyl) amino group, a di-C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamido 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 benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound are particularly preferably selected from 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, A-hydroxy-2 -meihoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-tri- hydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5- Bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 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-hydroxybenzaldehyde 2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxy- benzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzdehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxbenzaldehyde, 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-methyl -benzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 2,4-dihydroxy-6-methoxy-beπzaldehyd, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde , 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy 2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2 , 4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 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 -dihydroxybenza! dehyd, 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, 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-naphthene aldehyde, 4-dimethylamino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, A-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxybenzaldehyde 5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5- Chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4- Dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, A-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- (1-imidazolyl ) -benzaldehyde, pi peronal, 5-formyl-2-hydroxybenzoic acid, 5-formyl-2-hydroxy-3-methoxybenzoic acid, 5-formyl-2-hydroxy-3-methylbenzoic acid and 3-ethoxy-5-formyl-2-hydroxybenzoic acid. These representatives are also the most preferred additional reactive carbonyl compounds.

The reactive carbonyl component most preferably used is 2,4-dihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, A-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde , 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-cinnamic aldehyde, 4-hydroxy-3-methoxycinnamaldehyde, A-formyl-1-methylquinolinium p-toluenesulfonate and / or indole-3-carboxaldehyde.

The hair colorants of the invention preferably contain the reactive carbonyl component in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total colorant.

It may be advantageous for extending the color spectrum that the agents according to the invention furthermore comprise at least one component C different from the 1,3-dihydroaza-2H-indol-2-one derivatives of the formula (I), selected from (a) CH -acid compounds and (b) compounds having primary or secondary amino or hydroxy groups selected from aromatic hydroxy compounds, primary or secondary aromatic amines and nitrogen-containing heterocyclic compounds. The additional CH-acidic compounds of component C are preferably selected from the group consisting of physiologically compatible anions, in particular p-toluenesulfonates, methanesulfonates, hydrogensulfates, tetrafluoroborates and halides, such as the chlorides, bromides and iodides, formed salts of 1, 4- Dimethylquinolinium, 1-ethyl-4-methyl-quinolinium, 1-ethyl-2-methylquinolinium, 1, 2,3,3-tetramethyl-3H-indolium, 2,3-dimethylbenzothiazolium, 2,3-dimethylnaphtho [ 1,2-d] thiazolium, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium, 3-ethyl-2-methyl-benzoxazolium, 1,2,3-thymethylquinoxaluminum, 3-ethyl-2- Methyl-benzothiazolium, 1, 2-Dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium, 1, 2 Dihydro-4,6-dimethyl-1,3-dipropyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium, 1,2-dihydro-1, 3,4,5,6-pentamethyl-2-oxopyrimidinium, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo -pyrimidiniums, 2,5-dimethyl-3- (2-propenyl) -1, 3,4-thiadiazoliums, 3-ethyl-2,5-dimethyl-1, 3,4-thiadiazoliums, 1, 2

Dimethylchinolinium 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-dicyanomethyleneindan-1-one, 2- (2-furanoyl) acetonitrile, 2- (2-theonyl) acetonitrile, 2- (cyanomethyl) benzimidazole, 2- (cyanomethyl) benzothiazole and 2- (2,5-dimethyl-3-furanoyl) acetonitrile.

The additional compounds of component C selected from aromatic hydroxy compounds, primary or secondary aromatic amines and nitrogen-containing heterocyclic compounds are preferably compounds enumerated in the first embodiment as a developer component, provided that it is a primary or secondary amino or hydroxy group exhibit.

As component C, preference is given to using primary aromatic amines 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-di-methyl-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 (.beta.-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (.beta.-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 amine, 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- (.beta.-hydroxyethyloxy) -p-phenylenediamine, 2- (.beta.-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (i H -imidazol-1-yl) propyl] amine and 5,8-diaminobenzo-1, 4 dioxane and their physiologically acceptable salts.

Most particularly preferred as component C are the primary aromatic amines p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis - (beta-hydroxyethyl) -p-phenylenediamine.

As component C it is also possible to use aromatic primary amines which contain at least two aromatic nuclei.

Particular examples of preferred binuclear compounds include: 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 (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N 'bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4- diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis (2 ', 5'-diaminophenyl) - 1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particular preference as component C used binuclear amines are N ₁ N'-bis (.beta.-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 ^L , 5'-diaminophenyl) -1 , 4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

Further mentioned as component C p-aminophenol derivatives or one of their physiologically acceptable salts, preferably p-aminophenol, 4-amino-3-methylphenol, 4-Amtπo-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino 3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, A-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2 amino- methylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenot, 4-amino-2-fluoropheno !, 4-amino 2-chlorophenol, 4-amino-2,6-di-chlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.

In addition, heteroaromatic primary amines can be used as component C, for example pyridine, pyrimidine, pyrazole, pyrazolopyrimidine derivatives having at least one primary amino group, and their physiologically tolerated salts.

The agent according to the invention of the second embodiment, comprising at least one 1,3-dihydroaza-2H-indol-2-one derivative of the formula (I) and at least one reactive carbonyl compound may moreover also contain one or more developer components and / or one or more others Coupler components included. Suitable and preferred developer components and coupler components are the compounds which have already been mentioned in the context of the description of the first embodiment of the agents according to the invention. In this case, the 1, 3-dihydroaza-2H-indol-2-one derivative of the formula (I) has both the function of a CH-acidic compound and the function of a coupler component.

In addition to the abovementioned components, the colorants according to the invention may contain at least one precursor of a naturally-analogous dye. As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. In the form of etherification or esterification of the hydroxyl group or alkylation of the amino group. In a further preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

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

in the independently of each other

A ¹ is hydrogen, a C _r C ₄ -alkyl group or a C _r C ₄ -hydroxy-alkyl group,

A ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

A ³ is hydrogen or a C 1 -C ₄ -alkyl group, and

Each of A ⁴ and A ⁵ is independently hydrogen, a C ₁ -C ₄

Alkyl group or a group -CO-A ⁶ , in which A ⁶ is a C _r C ₄ alkyl group, and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Preferred derivatives of indoline are the 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 (IIb),

where the radicals A ¹ , A ² , A ³ , A ⁴ and A ^{5 have} the meanings given above, and physiologically tolerable salts of these compounds with an organic or inorganic acid. 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 may be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; Very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.

In a further preferred embodiment of the present invention, the colorants according to the invention may contain one or more substantive dyes for shading. Direct dyes are usually 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 (.beta.-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (.beta.-hydroxyethyl) -aminophenol, 2 (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-Amino-4- (2'-hydroxyethyl) -amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2 -nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4 -Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Furthermore, the agents according to the invention may 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 ^"

Cl ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct 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 agents of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

It is not necessary for the stated dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair dyeing and tinting compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermato- • ogy" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic products". Rohstoffe ", published by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

The colorants of the invention may further contain all known for such preparations active ingredients, additives and excipients. In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps )

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16, acylsarcosides having 10 to 18 C Atoms in the acyl group, acyl taurides having 10 to 18 carbon atoms in the acyl group, acyl isethionates having 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethylester with 8 up to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 C atoms, linear α-olefin sulfonates having 12 to 18 C atoms, Alpha sulfo fatty 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 which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 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 2-15 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 1 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 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 glyceryls,

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

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R '. 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.

And C _O alkyl groups, consisting essentially of C ₁₂ - - and C ₁₄ alkyl groups, essentially of C ₈ - to C ₁₆ -alkyl groups or C essentially of alkyl polyglycosides are those in which R ^J essentially of C ₈ are particularly preferred ₁₂ - to C ₁₆ alkyl groups.

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

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

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 ingredient of the preparations according to the invention in the event that an effect of a perfume oil on the hair which exceeds the duration of the hair treatment is desired. 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 those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ⁹ or -SO ₃ ^ -GrUpPe. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyldimethylammoniumglycinate, and 2-alkyl-3-carboxy-methyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ -Cis-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 for the formation of 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-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and

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

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

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred 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 trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-ethyl Palmitoyloxy-) dimethylammoniurnchlorid, 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 name Tegoamid ^® S 18 commercially stearamidopropyl di- represents methylamine.

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

Also suitable 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; diquaternary polydimethylsiloxanes Quatemium- 80).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl GIu- Ceth-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 is preferred.

Furthermore, the colorants of the invention can be further active ingredients, auxiliaries and additives, such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers , Acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate Copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate γ-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, Thickeners 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. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, such as soybean lecithin, egg lecithin and cephalins,

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

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl -2-alkylimidazolinium methosulfate defoamers such as silicones,

Dyes for staining the agent,

Antidandruff active ingredients such as Piroctone Olamine, zinc Omadine and Climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,

Active substances, such as allantoin, pyrrolidonecarboxylic acids and their salts, and also bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root, cholesterol, bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

Fatty acid alkanolamides,

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

- swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

- pigments,

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

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

- Antioxidants, included.

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

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

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 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. On the presence of oxidizing agents, for. B. H ₂ O ₂ , can be dispensed with, especially if the agent according to the invention contains no oxidation dye precursors. Even if the agent according to the invention contains oxidizable oxidation dye precursors or indole or indoline derivatives in air, oxidizing agents can be dispensed with without problems in such a case. However, it may u. It may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the invention for achieving the shades that are lighter than the keratin-containing fiber to be dyed. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, 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. 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 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 oxido reductases 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 particular embodiment of the present invention, the agent for dyeing nucleated fibers therefore contains at least one oxidizing agent, in particular H ₂ O ₂ , preferably in an amount of from 0.01 to 6% by weight, based on the total agent.

In the event that the agent according to the invention contains an oxidizing agent, the actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Unless explicitly stated otherwise, the pH values given in this document are to be understood as the pH values at 25 ° C. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can be in a range between 15 and 40 ⁰ C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

Especially with hair that is difficult to dye, the preparation with the dye precursors can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further period of exposure of 10 to 20 minutes, then rinsed and nachshampooniert if desired. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent. A second subject of the present application is the use of the agents according to the invention for dyeing keratinic fibers.

A third object of the present invention is a process for dyeing keratinic fibers, in particular human hair, wherein an agent according to the invention is applied to the keratinic fibers and rinsed out again after a contact time or washed out with a shampoo.

The invention will be further elucidated on the basis of the following examples, wherein the examples are intended to facilitate the understanding of the principle according to the invention and are not to be understood as limiting the general subject matter of the invention.

embodiments

1 1, 3-dihydroaza-2H-indole-2-ones as coupler component

1.1 Preparation of the colorants

For the preparation of the dyeing cream 50 g of a cream base were weighed into a 250 ml beaker and melted at 80 ⁰ C. The cream base used had the following composition:

Hydrenol ^® D ¹ 17.0 wt .-%

Lorof tech. ² 4.0% by weight

Texapon ^® NSO ³ 40.0% wt .-

Dehyton ^® K ⁴ 25.0 wt .-%

Eumulgin ^® B2 ⁵ 1, 5 wt .-%

Water 12.5% by weight

¹ Ci ₆ - ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)

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

⁴ N, N-dimethyl-N- (C _8- i ₈ -cocoamidopropyl) ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

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

In each case 1/400 mole of the 1, 3-dihydroaza-2H-indol-2-one derivative or the developer component was suspended separately in distilled water or dissolved by heating. Then ammonia (<1 ml, 25% ammonia solution) was added until the pH was between 9 and 10.

The dissolved dye precursors were incorporated successively into the hot cream. It was then made up to 97 g with distilled water and adjusted to a pH of 9.5 with ammonia. After filling with distilled water to 100 g, the mixture was stirred cold (<30 ° C), resulting in a homogeneous cream. 1.2 colorations

For the dyeings, 25 g of dyeing cream were mixed with 25 g of a 6% strength by weight aqueous hydrogen peroxide solution (unless stated otherwise).

One strand of hair (80% gray, 330 mg to 370 mg heavy) was added to each of the mixtures thus obtained. Subsequently, the mixtures and the hair strands were placed on a watch glass and the hair strands well embedded in the dyeing creams. After 30 minutes (± 1 minute) Reaction time at room temperature were removed and the strands of hair so washed many times, until the color was removed with an aqueous excess Texapon EVR ^® solution. ⁶ The strands of hair were air-dried and their color was determined and recorded under the daylight lamp (color tester HE240A) (Taschenlexikon der Farben, A. Komerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag, Zurich, Göttingen).

⁶ lauryl ether sulfate sodium salt with special additives (about 34 to 37%

Active substance content; INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis)

The results obtained in the staining investigations are shown in Table 1 below, wherein as 1,3-dihydroaza-2H-indol-2-one 1, 3-dihydro-4-aza-2H-indol-2-one (Compound A) or 1, 3-dihydro-7-aza-2H-indol-2-one (compound B) was used:

Table 1 :

2 1, 3-Dihydroaza-2H-indole-2-ones as CH-acidic compound

2.1 Preparation of the colorants

Aqueous gel formulation for the CH-acidic compound Gel 1:

CH-acidic compound 10 mmol Natrosol HR 250 2 g water, fully desalted ad 100 g

The CH-acidic compound was first dissolved with stirring in a little water, then made up to 98 g with water. With stirring, the Natrosol was added and the end of the swelling process was awaited.

Aqueous gel formulation for the reactive carbonyl compound Gel 2:

Carbonyl compound 10 mmol

Natrosol HR 250 2 g

NaOH (50% aqueous solution) possibly a few drops

Water, demineralized ad 100 g

The carbonyl compound 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 solution of the carbonyl compound (partially with gentle warming to about 40 ⁰ C). Subsequently, the Natrosol was added while stirring and the swelling process was awaited. 2.2 colorations

There were prepared aqueous gel formulations according to item 2.1 (Gel 1 and Gel 2) with the dye precursor combinations of Table 2. The gels were mixed at a weight ratio of 1: 1, then the pH was adjusted to 9 with a 10% by weight aqueous NaOH solution. The dye precursors were used in the combinations listed in Table 2.

The ready-to-use hair dye obtained was 90% gray on a tress, applied to previously untreated human hair (liquor weight ratio: gel mixture to hair = 2 to 1) and evenly distributed with an applicette. After an exposure time of 30 minutes at 32 ⁰ C, the tress was rinsed with lukewarm water and then dried in a stream of warm air (3O ⁰ C to 40 ⁰ C). The stains were assessed under a daylight lamp. The results obtained in the staining studies are shown in Table 2 below, wherein as 1,3-dihydroaza-2H-indol-2-one 1, 3-dihydro-4-aza-2H-indol-2-one (Compound A) or 1, 3-dihydro-7-aza-2H-indol-2-one (compound B) was used:

Table 2:

Claims

Patent claims

1. An agent for dyeing keratinic fibers, in particular human hair, comprising in a cosmetically acceptable carrier at least one 1, 3-dihydroaza-2H-indol-2-one derivative of the formula (I) and / or the physiologically tolerated salts thereof,

in which

R ¹ is N or CR ⁶ ,

R ² is N or CR ⁷ ,

R ³ is N or CR ⁸ ,

R ⁴ is N or CR ⁹ ,

with the proviso that exactly one of the groups R ¹ , R ² , R ³ or R ^{4 is} N,

R ⁵ is hydrogen, a branched or unbranched linear or cyclic C ₁ - to C ₆ -alkyl group, a C ₁ - to C ₆ -monohydroxyalkyl group, a C ₂ - to C ₆ -dihydroxyalkyl group, a C ₂ -C ₆ - Alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an arylC _r C ₆ alkyl group, a Ci-C ₆ alkoxy C _r C ₆ alkyl group, a group R ¹ R ¹¹ N- (CH ₂ ) _m -, wherein R ¹ and R "are independently a hydrogen atom, a C _r C ₄ alkyl group, a C _r C ₄ hydroxyalkyl group or an aryl-C _r C ₆ alkyl group, wherein R ¹ and R" together with the Nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and

R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, halogen, hydroxy, nitro, carboxy, branched or unbranched linear or cyclic C ₁ to C ₆ alkyl, C ₁ - to C ₆ monohydroxyalkyl group, a C ₂ to C ₆ dihydroxyalkyl group, a C ₂ -C ₆ alkenyl group, a branched or unbranched C _r to C ₆ alkoxy group, an optionally substituted aryl group, an optionally substituted one Heteroaryl group, an arylC _r C ₆ alkyl group, a C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl group, a group R ^l R ^ll N- (CH ₂ ) _m -, wherein R ¹ and R ¹¹ independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ¹ and R ¹¹ together with the nitrogen atom are a 5-, 6- or 7- and m is a number 2, 3, 4, 5 or 6.

2. Composition according to claim 1, characterized in that it contains a 1, 3-dihydroaza-2H-indol-2-one derivative of the formula (I), wherein R ^{5 is} hydrogen, methyl or ethyl.

3. Composition according to one of claims 1 or 2, characterized in that it contains a 1, 3-dihydroaza-2H-indol-2-one derivative of the formula (I), wherein R ¹ or R ^{4 are} nitrogen.

4. Composition according to one of claims 1 to 3, characterized in that it contains a 1, 3-dihydroaza-2H-indol-2-one derivative of the formula (I), wherein the respectively present radicals R ⁶ , R ⁷ , R ⁸ and R ^{9 are} hydrogen.

5. Composition according to one of claims 1 to 4, characterized in that it contains at least one developer component.

6. A composition according to claim 5, characterized in that it is in the developer component to a primary aromatic amine with another, located in the para or ortho position, free or substituted hydroxy or amino group, a Diaminopyridinderivat, a heterocyclic hydrazone, a 4-aminopyrazole derivative or a 2,4,5,6-tetraaminopyrimidine derivative.

7. Composition according to one of claims 1 to 6, characterized in that it further contains at least one of the 1, 3-dihydroaza-2H-indol-2-one derivatives of the formula (I) different coupler component.

8. Composition according to one of claims 1 to 7, characterized in that it contains at least one reactive carbonyl compound.

9. Composition according to claim 8, characterized in that it is the reactive carbonyl compound is an aromatic aldehyde, which is selected from the group formed by benzaldehyde, cinnamaldehyde, naphthaldehyde and derivatives thereof.

10. Composition according to one of claims 1 to 9, characterized in that it further comprises at least one of the 1, 3-dihydroaza-2H-indol-2-one derivatives of the formula (I) different compounds selected from (a) CH-acidic compounds and (b) compounds having primary or secondary amino or hydroxy groups selected from aromatic hydroxy compounds, primary or secondary aromatic amines and nitrogen-containing heterocyclic compounds.

11. Composition according to one of claims 1 to 10, characterized in that it further contains at least one substantive dye.

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

13. Use of a composition according to any one of claims 1 to 12 for dyeing keratinic fibers, in particular of human hair.

14. A process for dyeing keratinic fibers, in particular human hair, characterized in that an agent according to any one of claims 1 to 12 applied to the keratinic fibers and rinsed again after a contact time or washed out with a shampoo.