DE102006052283A1 - Composition for dyeing keratin fibers, particularly human hair, comprises at least one new cationic 3-oxo-dihydro-benzofuran, -benzothiophene or -indole derivative - Google Patents

Abstract

Composition (A) for dyeing keratin-containing fibers, especially human hair, comprises, in a cosmetic carrier, at least one cationic 3-oxo-2,3-dihydro-benzofuran, -benzothiophene or -indole derivative (I) and/or its enol. Composition (A) for dyeing keratin-containing fibers, especially human hair, comprises, in a cosmetic carrier, at least one cationic 3-oxo-2,3-dihydro-benzofuran, -benzothiophene or -indole derivative of formula (I) and/or its enol three of R1-R4 : H, halo, hydro, cyano, nitro, carboxy, sulfonamido, 1-6C alkyl or alkoxy, 2-6C alkenyl, optionally substituted aryl or heterocyclyl, aryl(1-6C)alkyl, 2-6C hydroxyalkoxy or (poly)hydroxyalkyl, or R'R''N-(CH 2) m-, and the last of these four groups is a substituent that carries a quaternary nitrogen; R' and R'' : 1-6C alkyl or alkenyl or aryl(1-6C)alkyl, or together they complete a 5-7 membered ring; m : 0-6; X : O, S or NR5; R5 : H, 1-6C alkyl, 2-6C alkenyl, aryl(1-6C)alkyl, 2-6C (poly)hydroxyalkyl or 1-6C alkoxy(2-6C)alkyl; An : physiologically tolerable anion. An independent claim is included for (I) as new compounds. [Image].

Description

The Invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, the special, cationic derivatives Benzofuran-3 (2H) -one or benzothiophene-3 (2H) -one or the Contains 1,2-dihydro-3H-indol-3-one, the use of these derivatives in agents for dyeing keratin-containing fibers, for color refreshing or shading of already colored keratin-containing Fibers and a method of dyeing of keratinous fibers, in particular human hair.

For dyeing keratin-containing fibers are generally either direct-acting Dyes or oxidation dyes produced by oxidative coupling one or more developer components with each other or with one or more coupler components arise for use. Coupler and developer components are also known as oxidation dye precursors designated.

When Developer components are usually primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Specific Representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-Dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 4,5-diamino-1- (2-hydroxyethyl) pyrazole.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. As coupler substances Particularly suitable are 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 (Lehmanns 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-methyl, 5-methylresorcinol, 3-amino-6-methoxy-2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

Regarding other usual ones Dye components becomes explicit to the series "Dermatology", issued by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, ch. 7, pages 248-250 (Direct Dyeing), and Chap. 8, pages 264-267 (oxidation dyes), as well as the "European Inventory of cosmetic raw materials ", 1996, published by the European Commission, available in Diskette form of the Federal Association of German industrial and commercial enterprises for medicines, Health food and personal care products e.V., Mannheim.

Although intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H ₂ O ₂ , which in some cases may result in damage to the fiber. Still problematic is the provision of oxidation hair dyeings in the red region with sufficient fastness properties, in particular with very good washing and rubbing fastnesses. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on persons with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage lies in the fact that the dyes often have only insufficient fastness properties.

In Patent applications WO-A1-02 / 22092 and WO-A2-02 / 00180 are indigo derivatives as a component in colorants for keratin-containing Fibers proposed. These indigo derivatives carry no substituents, which have a quaternized nitrogen atom.

The Patent Application WO-A2-00 / 38638 relates to colorants for keratin-containing fibers, in Among others, benzofuran derivatives in combination with reactive Carbonyl compounds are included. The affected benzofuran derivatives do not bear a substituent with a quaternized nitrogen atom.

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

worin

• • drei der Reste R1, R2, R3 und R4 stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine Hydroxygruppe, eine Cyanogruppe, eine Nitrogruppe, eine Carboxylgruppe, eine Sulfonamidogruppe, eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkoxygruppe, eine (C₂-C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, einen gegebenenfalls substituierten Heterozyklus, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkyloxygruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₂-C₆)-Polyhydroxyalkylgruppe oder eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkenylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6, und der übrige Rest aus R1, R2, R3 oder R4 steht für einen Substituenten, enthaltend ein quaterniertes Stickstoffatom,
• • X für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR5 steht, worin R5 ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₁-C₆)-Alkoxy-(C₂-C₆)-alkylgruppe oder eine (C₂-C₆)-Polyhydroxyalkylgruppe bedeutet und,
• • An^– für ein physiologisch verträgliches Anion steht.

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

wherein

• • three of the radicals R1, R2, R3 and R4 independently of one another represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfonamido group, a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) alkoxy group, a (C ₂ -C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) -Hydroxyalkyloxy group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II are each independently a (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkenyl group or an aryl C ₁ -C ₆ alkyl group, wherein R ^I and R ^II together with the nitrogen atom, a 5-, 6- or Can form a 7-membered ring and m is a number 0, 1, 2, 3, 4, 5 or 6, and the remainder of R1, R2, R3 or R4 is a substituent containing a quater nitrogen atom,
• X is an oxygen atom, a sulfur atom or a group NR5, in which R5 is a hydrogen atom, a (C ₁ -C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -alkenyl group, an aryl- (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₁ -C ₆ ) -alkoxy (C ₂ -C ₆ ) -alkyl group or a (C ₂ -C ₆ ) -polyhydroxyalkyl group, and
• • An ^{- stands} for a physiologically compatible anion.

Under Keratin fibers are wool, furs, feathers and in particular to understand human hair. The colorants of the invention can but in principle also for dyeing other natural fibers, such. As cotton, jute, sisal, linen or Silk, modified natural fibers such. Regenerated cellulose, nitro, Alkyl or hydroxyalkyl or acetyl cellulose can be used.

substituents, containing a quaternized nitrogen atom are by definition Substituents containing a permanently cationic nitrogen atom. The covalently bonding groups to the quaternized nitrogen atom are all different from hydrogen. The cationic Charge of the said nitrogen atom carries the one noted in formula (I) positive charge.

Prefers in the inventive compositions contained compounds according to formula (I) and / or their enol forms are those in which X is an oxygen atom stands.

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

• – drei der Reste R1, R2, R3, R4 für ein Wasserstoffatom stehen und der übrige der Reste R1, R2, R3, R4 für einen Substituenten, enthaltend ein quaterniertes Stickstoffatom, steht,
• – X für ein Sauerstoffatom steht, und
• – An^– ein physiologisch verträgliches Anion bedeutet.

The agent according to the invention particularly preferably contains at least one cationic compound of formula (I) and / or its enol form, in which

• Three of the radicals R 1, R 2, R 3, R 4 represent a hydrogen atom and the remainder of the radicals R 1, R 2, R 3, R 4 is a substituent containing a quaternized nitrogen atom,
• - X is an oxygen atom, and
• - An ^{- means} a physiologically acceptable anion.

in der
R6 ein Substituent, enthaltend ein quaterniertes Stickstoffatom, bedeutet und
An^– für ein physiologisch verträgliches Anion steht.Accordingly, agents preferred according to the invention comprise as cationic compound of the formula (I) at least one compound according to formula (I-1) and / or its enol form,

in the
R6 represents a substituent containing a quaternized nitrogen atom, and
An ^{- stands} for a physiologically acceptable anion.

In a preferred embodiment of the cationic organic compounds of this invention, in both formula (I) and formula (I-1), a substituent containing a quaternized nitrogen atom is an N, N, N-tri- (C ₁ to C ₆ ) -alkylammonio (C ₁ to C ₆ ) alkyl group (see formula (S-1) as an example of an N, N, N-trimethylammonio (C ₁ to C ₆ ) alkyl group, vide infra), an N , N, N-tri (C ₁ to C ₆ ) alkylammonio (C ₂ to C ₆ ) alkoxy group (see formula (S-2) as an example of an N, N, N-trimethylammonio (C ₂ to C ₆ ) alkoxy group, vide infra), an ω- (pyridinium-1-yl) - (C ₁ to C ₆ ) alkyl group (see formula (S-3), vide infra), an ω- (pyridinium-1 -yl) - (C ₁ to C ₆ ) alkoxy group (see formula (S-4), vide infra), an ω- (pyrimidinium-1-yl) - (C ₁ to C ₆ ) alkyl group, an ω- (Pyrimidinium-1-yl) - (C ₁ to C ₆ ) alkoxy group, a ω- (3- (C ₁ to C ₆ ) alkylimidazolium-1-yl) - (C ₁ to C ₆ ) alkyl group (see Formula (S-5) as an example of a ω- (3-methylimidazole ium-1-yl) - (C ₁ to C ₆ ) -alkyl group, vide infra), a ω- (3- (C ₁ to C ₆ ) -alkylimidazolium-1-yl) - (C ₁ to C ₆ ) - alkoxy group (see formula (S-6) as an example of a ω- (3-methylimidazolium-1-yl) - (C ₁ to C ₆ ) alkoxy group, vide infra), an ω- (3- (C ₁ to C ₆₎ -Hydroxyalkylimidazolium-1-yl) - alkyl or (C ₁ to C ₆₎ a ω- (3- (C ₁ to C ₆₎ -Hydroxyalkylimidazolium-1-yl) - (C ₂ to C ₆₎ alkoxy , Again, the N, N, N-tri- (C ₁ to C ₆ ) -alkylammonio (C ₂ to C ₆ ) alkoxy group, an ω- (pyridinium-1-yl) - (C ₁ to C ₆ ) alkoxy group, an ω- (pyrimidinium-1-yl) - (C ₁ to C ₆ ) alkoxy group, an ω- (3- (C ₁ to C ₆ ) alkylimidazolium-1-yl) - (C ₁ to C ₆ ) alkoxy group or a ω- (3- (C ₁ to C ₆ ) -hydroxyalkylimidazolium-1-yl) - (C ₂ to C ₆ ) alkoxy group particularly preferred substituents containing a quaternized nitrogen atom.

worin jeweils die Zahl n eine ganze Zahl von 1 bis 6 bedeutet. Die kationische Ladung der quaternierten Stickstoffatome der Substituenten (S-1) bis (S-6) sitzt am jeweiligen quaternierten Stickstoffatom des jeweiligen Substituenten. Die Kennzeichnung dieser kationischen Ladung wird bereits allgemein in Formel (I) bzw. Formel (I-1) vorgenommen und fehlt daher in den Formeln (S-1) bis (S-6). Die Substituenten der Formeln (S-2), (S-4) und (S-6) sind besonders bevorzugte Substituenten, enthaltend ein quaterniertes Stickstoffatom.It is preferred according to the invention if the substituent containing a quaternized nitrogen atom of the formula (I) or of the formula (I-1) is a substituent of the formulas (S-1) to (S-6)

wherein each n represents an integer of 1 to 6. The cationic charge of the quaternized nitrogen atoms of the substituents (S-1) to (S-6) is located at the respective quaternized nitrogen atom of the respective substituent. The labeling of this cationic charge is already generally carried out in formula (I) or formula (I-1) and therefore is absent in the formulas (S-1) to (S-6). The substituents of the formulas (S-2), (S-4) and (S-6) are particularly preferable substituents containing a quaternized nitrogen atom.

By definition, the physiologically acceptable anions An ^- according to formula (I) or formula (I-1) may not only carry a negative charge, but may also have a charge number greater than one. In the latter case the anions to be ^- the salt form to maintain electrical neutrality by formulating a stoichiometric coefficient of less than 1 described before the description of the anion. The physiologically acceptable anions are preferably selected from halide, 0.5 sulfate, hydrogen sulfate, 0.5 carbonate, bicarbonate, 1/3 phosphate, 0.5 hydrogen phosphate, p-toluenesulfonate, methyl sulfonate, trifluoromethanesulfonate, benzenesulfonate, dihydrogen phosphate or carboxylate (such as acetate, lactate, citrate or tartrate). Particularly preferably, An ^- in the formulas (I) and (I-1) is chloride, bromide, 0.5 sulfate, hydrogensulfate, acetate, p-toluenesulfonate, methylsulfonate, trifluoromethanesulfonate or benzenesulfonate.

It is preferred if the substituent containing a quaternized nitrogen atom according to formula (I) or according to formula (I-1) is a trimethylammonium (C ₂ -C ₆ ) alkyl group (according to formula S-1, where n = 2 to 6) or a trimethylammonium (C ₂ -C ₆ ) alkoxy group (according to formula S-2, where n = 2 to 6).

In particular, it is preferable that the substituent containing a quaternized nitrogen atom of the formula (I) or the formula (I-1) means an N, N, N-trimethylammoniumethyloxy group or an N, N, N-trimethylammoniumpropyloxy group. The present counterion An ^- according to formula (I) or (I-1) in this case preferably represents a halide ion, particularly preferably a chloride or a bromide ion.

• Diese Salze enthalten jeweils das physiologisch verträgliche Anion An^–.

The agents according to the invention particularly preferably comprise at least one of the following compounds as a cationic organic compound of the formula (I) and / or its enol form:

• These salts each contain the physiologically acceptable anion An ^- .

The following are examples of the substituents that are valid for all formulas of this application, if listed in a corresponding formula and not explained in more detail:
Examples of C ₁ -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. The same examples without the methyl group apply to the C ₂ to C ₆ alkyl groups, respectively.

Examples of (C ₁ -C ₆ ) -alkoxy groups are methoxy, ethoxy and propoxy.

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

preferred optionally substituted aryl groups are phenyl, naphthyl and Biphenyl.

Preferred aryl (C ₁ -C ₆ ) alkyl groups are benzyl and 2-phenylethyl.

Further, as preferred examples of a C ₂ -C ₆ hydroxyalkyl group, there may be mentioned hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyethyl to be named.

A 2-hydroxyethyl group is particularly preferred.

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

Examples of a C ₂ -C ₆ polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

The amino, dimethylamino, diethylamino, methylamino, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, 2-methylaminoethyl, piperidinomethyl, pyrrolidinomethyl, and the morpholinomethyl groups are examples of a group R'R '' N- (CH ₂ ) _n -, with the piperidinomethyl and the 2-dimethylaminoethyl group being particularly preferred.

Examples of an N, N, N-tri (C ₁ to C ₆ ) alkylammonio (C ₁ to C ₆ ) alkyl group are the N, N, N-trimethylammonioethyl group, the N-ethyl-N, N-dimethylammonioethyl group which are N, N-diethyl-N-methylammonioe ethyl, N, N, N-trimethylammoniopropyl, N-ethyl-N, N-dimethylammoniopropyl, N, N-diethyl-N-methylammoniopropyl, N, N, N-trimethylammoniobutyl, N-ethyl-N, N -dimethylammoniobutyl group, the N, N-diethyl-N-methylammoniobutyl group.

Examples of an N, N, N-tri (C ₁ to C ₆ ) alkylammonio (C ₁ to C ₆ ) alkoxy group are the N, N, N-trimethylammonioethoxy group, the N-ethyl-N, N-dimethylammonioethoxy group , the N, N-diethyl-N-methylammonioethoxy group, the N, N, N-trimethylammoniopropoxy group, the N-ethyl-N, N-dimethylammoniopropoxy group, the N, N-diethyl-N-methylammoniopropoxy group, the N, N, N- Trimethylammoniobutoxygruppe, the N-ethyl-N, N-dimethylammoniobutoxy, the N, N-diethyl-N-methylammoniobutoxygruppe.

Examples of an ω- (pyridinium-1-yl) - (C ₁ to C ₆ ) -alkyl group are the pyridinium-1-yl-methyl group, 2- (pyridinium-1-yl) ethyl group, 3- (pyridinium-1 yl) propyl group, 4- (pyridinium-1-yl) butyl group, 5- (pyridinium-1-yl) pentyl group, 6- (pyridinium-1-yl) hexyl group.

Examples of an ω- (pyridinium-1-yl) - (C ₁ to C ₆ ) -alkoxy group are the pyridinium-1-yl-methoxy group, 2- (pyridinium-1-yl) ethoxy group, 3- (pyridinium-1 yl) propoxy group, 4- (pyridinium-1-yl) butoxy group, 5- (pyridinium-1-yl) pentoxy group, 6- (pyridinium-1-yl) hexoxy group.

Examples of an ω- (pyrimidinium-1-yl) - (C ₁ to C ₆ ) -alkyl group are the pyrimidinium-1-yl-methyl group, 2- (pyrimidinium-1-yl) ethyl group, 3- (pyrimidinium-1 yl) propyl group, 4- (pyrimidinium-1-yl) butyl group, 5- (pyrimidinium-1-yl) pentyl group, 6- (pyrimidinium-1-yl) hexyl group.

Examples of ω- (pyrimidinium-1-yl) - (C ₁ -C ₆₎ alkoxy group are the pyrimidinium-1-yl-methoxy, 2- (pyrimidinium-1-yl) ethoxy, 3- (1- pyrimidinium yl) propoxy group, 4- (pyrimidinium-1-yl) butoxy group, 5- (pyrimidinium-1-yl) pentoxy group, 6- (pyrimidinium-1-yl) hexoxy group.

Examples of an ω- (3- (C ₁ to C ₆ ) -alkylimidazolium-1-yl) - (C ₁ to C ₆ ) -alkyl group are the (3-methylimidazolium-1-yl) methyl group, 2- (3 Methylimidazolium-1-yl) ethyl group, 3- (3-methylimidazolium-1-yl) propyl group, 4- (3-methylimidazolium-1-yl) butyl group, 5- (3-methylimidazolium-1-yl) pentyl group, 6- (3-methylimidazolium-1-yl) -pentyl group; 3-methylimidazolium-1-yl) hexyl group, (3-ethylimidazolium-1-yl) methyl group, 2- (3-ethylimidazolium-1-yl) ethyl group, 3- (3-ethylimidazolium-1-yl) propyl group, 4- ( 3-ethylimidazolium-1-yl) butyl group, 5- (3-ethylimidazolium-1-yl) pentyl group, 6- (3-ethylimidazolium-1-yl) hexyl group.

Examples of a ω- (3- (C ₁ to C ₆ ) -alkylimidazolium-1-yl) - (C ₁ to C ₆ ) -alkoxy group are the (3-methylimidazolium-1-yl) methoxy group, 2 (3 Methylimidazolium-1-yl) ethoxy group, 3- (3-methylimidazolium-1-yl) propoxy group, 4- (3-methylimidazolium-1-yl) butoxy group, 5- (3-methylimidazolium-1-yl) pentoxy group, 6- (3-methylimidazolium-1-yl) -pentoxy group 3-methylimidazolium-1-yl) hexoxy group, (3-ethylimidazolium-1-yl) methoxy group, 2- (3-ethylimidazolium-1-yl) ethoxy group, 3- (3-ethylimidazolium-1-yl) propoxy group, 4- (3-ethylimidazolium-1-yl) -propoxy group 3-ethylimidazolium-1-yl) butoxy group, 5- (3-ethylimidazolium-1-yl) pentoxy group, 6- (3-ethylimidazolium-1-yl) hexoxy group.

Examples of a ω- (3- (C ₂ to C ₆ ) -hydroxyalkylimidazolium-1-yl) (C ₁ to C ₆ ) alkyl group are the (3- (2-hydroxyethyl) imidazolium-1-yl) methoxy group, 2- (3- (2-hydroxyethyl) imidazolium-1-yl) ethoxy group, 3- (3- (2-hydroxyethyl) imidazolium-1-yl) propoxy group, 4- (3- (2-hydroxyethyl) imidazolium-1 yl) butoxy group, 5- (3- (2-hydroxyethyl) imidazolium-1-yl) pentoxy group, 6- (3- (2-hydroxyethyl) imidazolium-1-yl) hexoxy group.

Examples of an ω- (3- (C ₁ to C ₆ ) -hydroxyalkylimidazolium-1-yl) - (C ₁ to C ₆ ) alkoxy group are the (3- (2-hydroxyethyl) imidazolium-1-yl) methoxy group, 2- (3- (2-hydroxyethyl) imidazolium-1-yl) ethoxy group, 3- (3- (2-hydroxyethyl) imidazolium-1-yl) propoxy group, 4- (3- (2-hydroxyethyl) imidazolium-1 yl) butoxy group, 5- (3- (2-hydroxyethyl) imidazolium-1-yl) pentoxy group, 6- (3- (2-hydroxyethyl) imidazolium-1-yl) hexoxy group.

The Compounds according to formula (I) are CH-acidic compounds. Colorants containing the compounds of Contain formula (I), color keratin-containing fibers already without the presence of other additives. When CH-acidic compounds generally become such compounds which is bound to an aliphatic carbon atom Carrying hydrogen atom, due to electron-withdrawing Substituents an activation of the corresponding carbon-hydrogen bond is effected.

The compounds of formula I are novel and can be provided, for example, according to the procedures of Synthesis Example 1 (vide infra). This synthetic route can be represented, for example, by the following synthesis scheme in which Hal is a halogen atom, in particular chlorine, bromine or iodine, X is as defined in formula (I) and R ^{7 is} a group containing a quaternized nitrogen atom:

dye, the as coloring Component containing compounds of formula I alone are preferred for dyeings used in the delicate yellow area. Dyeing with even greater brilliance and improved fastness properties (light fastness, wash fastness, Rubbing fastness) a wide range of shades from yellow to yellow-brown, orange, brown-orange, medium brown, dark brown, purple, dark purple to dark green brown and black are achieved when the compounds used in the invention of the formula I together with at least one reactive carbonyl compound (referred to below as component B) in the composition according to the invention is included.

• a) von Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente B leitet sich in diesem Fall c) von einem Aldehyd ab)

an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.Reactive carbonyl compounds as component B according to the invention have at least one carbonyl group as a reactive group which reacts with the CH-acidic compound of formula I to form a carbon-carbon bond. Preferred reactive carbonyl compounds are aldehydes and ketones. Furthermore, according to the invention, those compounds are also usable as component B in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with the CH-acidic compounds of the formula I is always present. These derivatives are preferably addition compounds

• a) amines and derivatives thereof to form imines or oximes as addition compound
• b) of alcohols to form acetals or ketals as addition compound
• c) of water with formation of hydrates as addition compound (component B is derived in this case c) from an aldehyde)

to the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred reactive carbonyl compounds of component B are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9 carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),
2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-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 trifluoroacetone, chromone-3-aldehyde, 3- (5'-nitro -2'-furyl) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 5- (4-dimethylaminophenyl) -penta-2,4-dienal, 5- (4-diethylaminophenyl) -penta- 2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2 , 4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal,
9-methyl-3-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, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-formyl-1 methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-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, 5-formyl-1-methyl-quinolinium, 6-formyl 1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-ben cylchinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium-benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin , 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

worin

• • R¹, R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Dialkylaminogruppe, eine Di(C₂-C₆-hydroxyalkyl)aminogruppe, eine Di(C₁-C₆-alkoxy-C₁-C₆-alkyl)aminoguppe, eine C₁-C₆-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine C₂-C₆-Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R⁴ und R⁵ stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

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

wherein

• R ¹ , R ² and R ³ are each independently hydrogen, halogen, C ₁ -C ₆ alkyl, hydroxy, C ₁ -C ₆ alkoxy, C ₁ -C ₆ dialkylamino, etc. 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 -C ₆ hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group , a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group, an acetyl group or a nitro group,
• Z 'is a direct bond or a vinylene group,
• R ⁴ and R ⁵ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component B are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1 naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo 4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2 -methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde , 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethyl benzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2 Hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2 , 3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde , 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde , 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3 -methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenz aldehyde, 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-dodecarbaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3 Chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4- Dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy 4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3 Hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4- Dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-carbo xy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy 5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde ( 3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal.

In a second embodiment it may be advantageous to extend the color spectrum, the agents according to the invention in addition to at least one compound according to formula (I) as a component A and at least one compound of component B at least one add further compound as component C. The connection of Component C is selected from CH-acidic compounds which are obtained from compounds of the formula (I) are different.

The additional CH-acidic compounds of component C are preferably selected from the group consisting of physiologically acceptable anions, in particular p-toluenesulfonates, Methanesulfonates, hydrogen sulfates, tetrafluoroborates and halides, such as the chlorides, bromides and iodides, formed salts of 1,4-dimethylchinolinium, 1-ethyl-4-methyl-chinoliniums, 1-ethyl-2-methylquinolinium, 1,2,3,3-tetramethyl-3H-indolium, 2,3-dimethyl-benzothiazoliums, 2,3-dimethyl-naphtho [1,2-d] thiazolium, 3-ethyl-2-methylnaphtho [1,2-d] thiazolium, 3-ethyl-2-methylbenzoxazoliums, 1,2,3-trimethylquinoxaluminiums, 3-ethyl-2-methylbenzothiazoliums, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium, 1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium, 1,2-dihydro-4,6-dimethyl-1,3-dipropyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium, 1,2-Dihydro-1,3,4,5,6-pentamethyl-2-oxo-pyrimidiniums, 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-dihydro-1- (2-hydroxyethyl) -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-thiadiazolium, 1,2-dimethylquinolinium and 1,3,3-trimethyl-2-methylenedoline (Fischer's base), as well as Oxindole, 3-methyl-1-phenyl-pyrazolin-5-one, indane-1,2-dione, indane-1,3-dione, Indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2- (2-furanoyl) acetonitrile, 2- (2-theonyl) acetonitrile, 2- (cyanomethyl) benzimidazole, 2- (cyanomethyl) benzothiazole and 2- (2,5-dimethyl-3-furanoyl) acetonitrile.

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

to Synthesis of the reaction products RP can be molar ratios of component B to the compound of formula I from about 1: 1 to about 2: 1 make sense.

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

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

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄-Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

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

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 -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, 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 each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals 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, in particular, the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, Imidazolinium and ammonium.

Especially preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-para-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- (ß, 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 Salt.

Very particular according to the invention preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It can continue according to the invention be preferred to use as a developer component compounds, which contain at least two aromatic nuclei which are reactive with amino and / or hydroxyl groups are substituted.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.

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 are 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 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 interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or C ₁ - to C ₈ alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another are 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 -aminoalkyl radical or a direct compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ alkyl radical, with the proviso that the compounds of the Formula (E2) contain only one bridge Y per molecule.

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

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 (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 tolerable Salts.

All particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, Bis- (2-hydroxy-5-aminophenyl) methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane or one their physiologically compatible Salts.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest,1 einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁- bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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, 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, C ₁ to C ₄ aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, 1 C ₁ to C ₄ hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl- (C ₁ - to C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl, and
• - G ¹⁴ represents a hydrogen or halogen 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, C ₁ to C ₄ aminoalkyl or C ₁ to C ₄ cyanoalkyl,
• 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 used in formula (E3) substituents are analogous to the invention to the above statements Are defined.

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-cuorophenol, 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-Cuorophenol, 4-Amino-2-chlorophenol, 4-Amino-2,6-dichlorophenol, 4-Amino-2- (diethylaminomethyl) -phenol as well as their physiologically tolerable Salts.

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

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

Farther For example, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

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 the German patent DE 2 359 399 , the Japanese Patent Application JP 02019576 A2 or in the laid-open specification 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 the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3 dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl 3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-one 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.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄- Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl radical, wherein the dialkyl radicals optionally 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] - (C ₁ - to C ₄ ) aminoalkyl radical,
• - the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) -aminoalkyl radical, wherein 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) aminoalkyl radical , an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) -amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• The sum of p + q is not equal to 0,
• If p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• When p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin; sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomeres Gleichgewicht vorhanden ist.

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

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

The Pyrazolo [1,5-a] pyrimidines of the above formula (E4) can be used as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

In a further preferred embodiment contain the colorants of the invention at least one coupler component.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, Resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-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)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxy-ethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol, 2-({3-[(2- Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-Hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]ethanol, 3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol sowie deren physiologisch verträglichen Salze.

According to preferred coupler components are

• - 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-diaminophenoxy-ethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino ) benzene, 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2- [3-morpholine-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-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylendioxybenzolderivate 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 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-chloro sorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

In addition, in the Frame a fifth embodiment preferred as precursors of natural dyes such indoles and Indolines in the inventive compositions be used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups can more Wear substituents, for. B. in the form of etherification or esterification the hydroxy group or an alkylation of the amino group. In a second preferred embodiment contain the colorants at least one indole and / or Indoline.

in der unabhängig voneinander

• – G²¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – G²² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – G²³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – G²⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-G²⁶, in der G²⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – G²⁵ steht für eine der unter G²⁴ genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

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

in the independently of each other

• G ²¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• G ²² is hydrogen or a -COOH group, where the -COOH group may also be 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 group, and
• - G ²⁵ is one of the groups mentioned under G ²⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially 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.

Especially noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

• – G²⁷ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – G²⁸ steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – G²⁹ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – G³⁰ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-G³², in der G³² steht für eine C₁-C₄-Alkylgruppe, und
• – G³⁰ steht für eine der unter G³⁰ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

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

in the independently of each other

• G ²⁷ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• G ²⁸ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• G ²⁹ is hydrogen or 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 ³⁰ stands for one of the groups mentioned in G ³⁰ ,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially 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.

Within of this group are N-methyl-5,6-dihydroxyindole, 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 in the colorants of the invention both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. The hydrochlorides, the sulfates and hydrobromides used. The indole or Indoline derivatives are common in these in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

• – Pyranose-Oxidase und z. B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

In a further embodiment, it is preferred to formulate the agent according to the invention free of oxidizing agents. On the presence of oxidizing agents, for. B. H ₂ O ₂ , can be omitted in particular if the agent according to the invention contains no oxidation dye precursors. If the agent according to the invention contains air-oxidizable oxidation dye precursors or indole or indoline derivatives, oxidizing agent can likewise be dispensed with without problems in such a case. However, it may u. It may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the invention for achieving the shades that are lighter than the keratin-containing fiber to be dyed. Oxidizing agents are generally used in an amount of 0.01 to 6 wt .-%, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ . Also, mixtures of several oxidizing agents, such as a combination of hydrogen peroxide and peroxodisulfates of ammonium, the alkali or alkaline earth metals, or, for example, iodide ion sources, such as. 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. Suitable enzymes are, for. As peroxidases, which 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, for. B.

• - pyranose oxidase and z. D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• Alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

In a further embodiment, the colorants according to the invention for further modifying the color shades in addition to the compounds according to the invention additionally contain conventional substantive dyes, such as nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1 , 4-diamino-2-nitroben zol, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4 Amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-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.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

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

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called.

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

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of group (c). The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are particularly preferred substantive dyes.

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

Farther can the preparations according to the invention also occurring in nature dyes, as for example in 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 required that the optionally containing direct dyes each uniform compounds represent. Rather, you can in the colorants according to the invention, due to the production process for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, eg. B. toxicological, must be excluded.

to Achieving further and more intense colorations can the agents of the invention additionally color enhancers contain. 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 Salt.

The above color amplifier can 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, be used.

The agents according to the invention can have a pH of from pH 4 to 12, preferably from pH 5 to 10.

The Colorants according to the invention already at physiologically acceptable temperatures of below 45 ° C intensive Colorations. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants may usually be in a hydrous cosmetic carrier be incorporated. Suitable hydrous cosmetic carriers are z. As creams, emulsions, gels or surfactant-containing foaming solutions such z. As shampoos or other preparations, for use on the keratin-containing Fibers are suitable. If necessary, it is also possible to dye in anhydrous carrier incorporate. Examples of further suitable and inventively more preferred Ingredients are given below.

When cosmetic carrier becomes according to the invention in particular an otherwise usual carrier of coloring agents used human hair. The colorants according to the invention can, apart from the Derivatives of the general formula (I) according to known colorants be composed or for this usual Contain ingredients.

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

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

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

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2 bis 15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

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

• - linear fatty acids with 10 to 22 carbon 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,
• Acyltaurides 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 alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-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 addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols having 8 to 22 carbon atoms.

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

Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _8-18 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C_12-22-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C_8-22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Anlagerungsprodukte von Ethylenoxid an Sorbitanfettsäureester
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide.

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

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• C _12-22 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - Addition products of ethylene oxide with sorbitan fatty acid esters
• - Addition products of ethylene oxide to fatty acid alkanolamides.

Examples for the in the hair treatment compositions according to the invention Usable cationic surfactants are especially quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further usable according to the invention cationic surfactants are the quaternized protein hydrolysates represents.

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, quaternium-80.).

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

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

An example of a cationic surfactant usable quaternary sugar derivative is the trade ^® product Glucquat 100 that according to CTFA name "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

at the compounds used as surfactants with alkyl groups each are uniform substances. However, it is usually preferred in the preparation of these substances of native vegetable or animal raw materials, so that you substance mixtures obtained with different, depending on the raw material alkyl chain lengths.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions 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.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallylammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylaminoethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazoliniummethochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methylmethacrylat/tert.-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.-Butylacrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Glucose und Maleinsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline, sowie Silikonöle,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsvermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – Antischuppenwirkstoffe wie Piroctone Olamine und Zink Omadine,
• – weitere Substanzen zur Einstellung des pH-Wertes, wie Ammoniak, Monoethanolamin, basische Aminosäuren und Citronensäure
• – Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze, Pflanzenextrakte und Vitamine,
• – Cholesterin,
• – Lichtschutzmittel,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsäureester,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate, Imidazole, Tannine, Pyrrol,
• – Trübungsmittel wie Latex,
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft sowie
• – Antioxidantien.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylate / 2-hydroxypropylmethacrylate copolymers,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as glucose and maleic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide 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 substances for adjusting the pH, such as ammonia, monoethanolamine, basic amino acids and citric acid
• - active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - sunscreen,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• Fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole,
• Opacifiers such as latex,
• Pearlescing agents such as ethylene glycol mono- and distearate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and
• - antioxidants.

The Components of the hydrous carrier become the preparation the colorant of the invention in for usual for this purpose Quantities used; z. B. become emulsifiers in concentrations from 0.5 to 30% by weight and thickener in concentrations of 0.1 to 25 wt .-% of the total colorant used.

For the dyeing result It may be advantageous to the colorants Add ammonium or metal salts. Suitable metal salts are z. B. formates, carbonates, halides, sulfates, butyrates, valerates, Capronates, Acetates, Lactates, Glycolates, Tartrates, Citrates, Gluconates, Propionates, phosphates and phosphonates of alkali metals, such as potassium, Sodium or lithium, alkaline earth metals, such as magnesium, calcium, Strontium or barium, or of aluminum, manganese, iron, cobalt, Copper or zinc, with sodium acetate, lithium bromide, calcium bromide, Calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, Ammonium carbonate, chloride and acetate are preferred. These salts are preferably in an amount of 0.03 to 10 wt .-%, in particular from 0.5 to 5% by weight, based on the ready-to-use colorant, contain.

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

wobei R1, R2, R3, R4, X und An^– wie im ersten Erfindungsgegenstand beschrieben definiert sind, bevorzugt zusammen mit mindestens einer reaktiven Carbonylverbindung als Komponente B, als färbende Komponente in Haarfärbemitteln.A second aspect of the present invention relates to the use of at least one compound according to formula I and / or its enol form,

where R1, R2, R3, R4, X, and An ^- are as defined in the first subject of the invention, preferably together with at least one reactive carbonyl compound as component B, as a coloring component in hair colorants.

In a preferred embodiment using those compounds of formula I as a coloring component in hair dyes, which are preferred from those named in the first subject of the invention and particularly preferred representatives. The same applies to the connections component B.

Furthermore it may be preferred at least one reaction product RP from a Compound according to formula I and a representative of component B as coloring components in hair dyes to use.

wobei R1, R2, R3, R4, X und An^– wie im ersten Erfindungsgegenstand beschrieben definiert sind, bevorzugt zusammen mit mindestens einer reaktiven Carbonylverbindung als Komponente B, auf die keratinhaltigen Fasern aufgebracht, einige Zeit, üblicherweise ca. 15-30 Minuten, auf der Faser belassen und anschließend wieder ausgespült oder mit einem Shampoo ausgewaschen wird. Während der Einwirkzeit des Mittels auf der Faser kann es vorteilhaft sein, den Färbevorgang durch Wärmezufuhr zu unterstützen. Die Wärmezufuhr kann durch eine externe Wärmequelle, wie z. B. warme Luft eines Warmluftgebläses, als auch, insbesondere bei einer Haarfärbung am lebenden Probanden, durch die Körpertemperatur des Probanden erfolgen. Bei letzterer Möglichkeit wird üblicherweise die zu färbende Partie mit einer Haube abgedeckt.A third aspect of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant containing at least one compound according to formula I and / or their enol form,

wherein R1, R2, R3, R4, X and An are ^- as defined in the first subject of the invention, preferably together with at least one reactive carbonyl compound as component B, applied to the keratin fibers, some time, usually about 15-30 minutes on leave the fiber and then rinsed again or washed out with a shampoo. During the exposure time of the agent on the Fa It may be advantageous to support the dyeing process by supplying heat. The heat can be supplied by an external heat source, such. B. warm air of a hot air blower, as well as, especially when a hair color on living subjects, done by the body temperature of the subject. In the latter case, usually the part to be dyed is covered with a hood.

If the compounds of formula (I) together with the reactive carbonyl compounds Component B find application, the compounds according to formula I or the compounds of component B, in particular the above named preferred and particularly preferred representatives, as a coloring Components are applied either simultaneously to the hair or in succession, d. H. in a multi-stage process. It does not matter which of the two components is applied first. The optionally contained ammonium or metal salts can thereby the compounds of formula I or the compounds of the component B be added. Between the application of the individual components can up to 30 minutes apart. Also a pretreatment of Fibers with the saline solution is possible.

• V1 vor der Anwendung des erfindungsgemäßen Mittels einer Blondierung oder
• V2 vor der Anwendung des erfindungsgemäßen Mittels einer oxidativen Färbung

unterzogen.Before applying the agent according to the invention in the process according to the invention, it may be desirable to subject the keratin-containing fiber to be dyed to a pretreatment. The time sequence of the pretreatment step required for this purpose and the application of the agent according to the invention need not be in immediate succession, but there may be a period of up to a maximum of two weeks between the pretreatment step and the application of the agent according to the invention. For this purpose, several pre-treatment methods are suitable. The fiber is preferred

• V1 before the application of the inventive bleaching agent or
• V2 before the application of the inventive agent of an oxidative dyeing

subjected.

in the Pretreatment V1 is the keratinhaltige fiber with a Bleaching agent treated. The Blondiermittel contains beside an oxidizing agent, as usual Hydrogen peroxide, preferably at least one as oxidation and bleach booster effective inorganic persalt, such as. B. a peroxodisulfate of Sodium, potassium or ammonium. colorations according to the method of the invention obtained by the pretreatment V1 a special brilliance and Color depth.

in the Pretreatment stage V2 is an agent containing the aforementioned Oxidation dye precursors as developer and optionally Coupler components and optionally the aforementioned derivatives of Indoles or Indolins applied to the fiber and after a contact time optionally with the addition of the abovementioned suitable oxidizing agents on the hair for Leave on the keratin fiber for 5-45 minutes. After that, the hair gets rinsed. By the subsequent Application of the agent according to the invention can present oxidation stains to be given a new shade of color. If you choose the color shade of the agent according to the invention in the same shade of oxidative staining, so may the coloration of existing oxidation dyes according to the inventive method be refreshed. It turns out that the color refreshment or Nuancierung according to the method of the invention a color refresh or nuance alone with conventional substantive dyes in color brilliance and color depth are superior is.

Contains the hair dye in addition to the compounds according to formula I and optionally the compounds of component B additionally as Oxidizing agent Hydrogen peroxide or a hydrogen peroxide-containing Oxidant mixture, so is the pH of the hydrogen peroxide-containing hair dye preferably in a pH range of pH 7 to pH 11, particularly preferred pH 8 to pH 10. The oxidizing agent can be used immediately before use with the hair dye mixed and the mixture applied to the hair. Become the compounds of the formula I and the component B in a two-stage Applied to the hair, the oxidizing agent is in one the two process steps together with the corresponding coloring Apply component. For this purpose, it may be preferable that Oxidizing agent with one of the coloring components in one To assemble containers.

The compounds of formula I and the compounds of component B can be stored either in separate containers or together in a container, either in a liquid to pasty preparation (aqueous or anhydrous) or as a solid, for example as a dry powder. If the components are stored together in a liquid preparation, it should be substantially anhydrous to reduce a reaction of the components and have an acidic pH. If the components are stored together, it is preferred to use them as a solid, in particular in the form of a preferred multilayer molded body, for. B. as a tablet. In the case of the multilayer molded bodies, the component A is incorporated in one layer and the component B in another layer, wherein between these layers is preferably a further layer as a release layer. The separating layer is free of compounds of components A and B.

at the separate storage, the reactive components are only immediately intimately mixed with each other before use. In the dry Storage usually becomes before use a defined amount of warm (30 ° C up to 80 ° C) Added water and a homogeneous mixture.

wobei R1, R2, R3, R4, X und An^– wie im ersten Erfindungsgegenstand beschrieben definiert sind, bevorzugt zusammen mit mindestens einer reaktiven Carbonylverbindung als Komponente B, zur Nuancierung von Oxidationsfärbungen von keratinhaltigen Fasern, insbesondere menschlichen Haaren. Bei der Verwendung ist es unerheblich, ob die Nuancierung gleichzeitig während der oxidativen Färbung erfolgt, oder die oxidative Färbung zeitlich vor der Nuancierung liegt.A fourth subject of the invention is the use of at least one compound according to formula I and / or its enol form,

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

wobei R1, R2, R3, R4, X und An^– wie im ersten Erfindungsgegenstand beschrieben definiert sind, bevorzugt zusammen mit mindestens einer reaktiven Carbonylverbindung als Komponente B zur Farbauffrischung von mit oxidativen Färbemitteln gefärbten keratinhaltigen Fasern.A fifth object of the invention is the use of at least one compound according to formula I and / or its enol form,

wherein R1, R2, R3, R4, X, and An ^- are as defined in the first subject of the invention, preferably together with at least one reactive carbonyl compound as component B for color refreshing keratin-containing fibers colored with oxidative coloring agents.

The colorations Keratinhaltiger fibers are known environmental influences, such as For example, light, friction or washes exposed and thereby lose in brilliance and color depth. Worst case arises if necessary, a nuance shift of the coloring. Such aged dyeings keratin-containing fibers, if the user wishes, by a color refreshing again almost in the color state be offset, as he is immediately after the original coloring presented. It is according to the invention, for such Color refreshment is a combination of at least one compound with the formula I, preferably in combination with at least one Use compound of component B.

worin

• • drei der Reste R1, R2, R3 und R4 stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine Hydroxygruppe, eine Cyanogruppe, eine Nitrogruppe, eine Carboxylgruppe, eine Sulfonamidogruppe, eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkoxygruppe, eine (C₂-C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, einen gegebenenfalls substituierten Heterozyklus, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkyloxygruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₂-C₆)-Polyhydroxyalkylgruppe oder eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkenylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6, und der übrige Rest aus R1, R2 R3 oder R4 steht für einen Substituenten, enthaltend ein quaterniertes Stickstoffatom,
• • X für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR5 steht, worin R5 ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₁-C₆)-Alkoxy-(C₂-C₆)-alkylgruppe oder eine (C₂-C₆)-Polyhydroxyalkylgruppe bedeutet und,
• • An^– für ein physiologisch verträgliches Anion steht.

A sixth subject of the invention are compounds of the formula (I) or their enol form

wherein

• • three of the radicals R1, R2, R3 and R4 independently of one another represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfonamido group, a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) alkoxy group, a (C ₂ -C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) -Hydroxyalkyloxy group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II are each independently a (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkenyl group or an aryl C ₁ -C ₆ alkyl group, wherein R ^I and R ^II together with the nitrogen atom, a 5-, 6- or Can form a 7-membered ring and m is a number 0, 1, 2, 3, 4, 5 or 6, and the remainder of R 1, R 2 R 3 or R 4 is a substituent containing a quaternary iert nitrogen atom,
• X is an oxygen atom, a sulfur atom or a group NR5, in which R5 is a hydrogen atom, a (C ₁ -C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -alkenyl group, an aryl- (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₁ -C ₆ ) -alkoxy (C ₂ -C ₆ ) -alkyl group or a (C ₂ -C ₆ ) -polyhydroxyalkyl group, and
• • An ^{- stands} for a physiologically compatible anion.

EXAMPLES Synthesis Example 1 Preparation of N, N, N-trimethyl-3 - [(3-oxo-2,3-dihydro-1-benzofuran-6-yl) oxy] propane ammonium bromide (A1)

A mixture of 14.7 g (95.8 mmol) of 6-hydroxybenzofuran-3 (2H) -one and 25.0 g (95.8 mmol) of 3-bromopropyltrimethylammonium bromide was dissolved in 500 ml of acetonitrile with the addition of 13.2 g ( 95.8 mmol) of potassium carbonate is refluxed for 8 hours. After cooling, the potassium carbonate was filtered off and the product was precipitated by the addition of ether. A powdery, orange-red solid precipitated, which was washed with ether and dried.
Yield = 14.7 g (46%)
¹ H-NMR (400 MHz, DMSO-d6): δ [ppm] = 2.21 (m, 2H); 3.17 (s, 9H); 3.55 (t, 2H); 4.21 (t, 2H); 4.79 (s, 2H); 6.11 (d, 1H); 6.87 (s, 1H); 7.54 (d, 1H)
13 C-NMR (400 MHz, DMSO-d6): δ [ppm] = 22.4; 33.5; 63.7; 65.2; 71.7; 98.0; 111.3; 114.8; 124.8; 166.2; 175.9; 197.1

Dyeing

First, the following compositions were prepared: Aqueous gel formulation for component A (Gel 1): Compound of formula (I) (component A) 10 mmol Natrosol HR 250 2.5 g isopropanol 10 g Water, demineralized ad 100 g

The compound of formula 1 (component A) was first dissolved or suspended with stirring in a little water and the isopropanol, then made up to 97.5 g with water. While stirring, the Natrosol was added and the swelling process was awaited. Aqueous gel formulation for component B (Gel 2): reactive carbonyl compound (component B) 10 mmol Natrosol HR 250 2 g NaOH (50% aqueous solution) maybe a few drops Water, demineralized ad 100 g

Of the aromatic aldehyde (component B) was dissolved in a little water or suspended. To increase the solubility was alkalized if necessary with a few drops of 50% sodium hydroxide solution. Subsequently was made up to 98 g with water and until the complete solution the aldehyde stirred (partially with gentle warming to about 40 ° C). Subsequently was stirring Added Natrosol and waited for the swelling process.

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

This ready-to-use hair dye thus obtained was applied to a hair strand of 90 gray, non-pretreated human hair (liquor weight ratio gel mixture / hair = 2: 1) and evenly distributed with an applicette. After a contact time of 30 minutes at 32 ° C, the tress was rinsed with lukewarm water and then dried in a stream of warm air. The stains were visually assessed under a daylight lamp. Component A (to Table 1): A1 N, N, N-trimethyl-3 - propanammoniumbromid [(3-oxo-2,3-dihydro-1-benzofuran-6-yl) oxy] Component B (to Table 1) B1 4-hydroxy-3-methoxybenzaldehyde (vanillin) B2 3-ethoxy-4-hydroxybenzaldehyde (ethylvanillin) B3 3,5-dimethoxy-4-hydroxybenzaldehyde B4 4-hydroxy-2-methoxybenzaldehyde B5 3,4-dihydroxy benzaldehyde B6 3,5-dimethyl-4-hydroxybenzaldehyde B7 4-Hydroxy-1-naphthaldehyde B8 4-diethylamino-2-hydroxybenzaldehyde B9 2,4-dihydroxybenzaldehyde

Table 1:

Claims (26)

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

in which three of the radicals R 1, R 2, R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfonamido group, a (C ₁ -C ₆ ) -alkyl group, a ( C ₁ -C ₆ ) alkoxy group, a (C ₂ -C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) -Hydroxyalkyloxy group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II are independently is a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -alkenyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ^I and R ^II together with the nitrogen atom are 5-, 6- or m is a 7-membered ring and m is a number 0, 1, 2, 3, 4, 5 or 6, and the remainder of R 1, R 2 R 3 or R 4 is a substituent containing a q nitrogen atom, X is an oxygen atom, a sulfur atom or a group NR5, wherein R5 is a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) alkenyl group, an aryl (C ₁ -C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₁ -C ₆ ) -alkoxy (C ₂ -C ₆ ) -alkyl group or a (C ₂ -C ₆ ) -polyhydroxyalkyl group and, An ^{- stands} for a physiologically acceptable anion. Composition according to claim 1, characterized in that in formula (I) X for an oxygen atom is. Composition according to one of claims 1 or 2, characterized in that they contain as cationic compound of the formula (I) at least one compound according to formula (I-1) and / or their enol form,

in which R 6 is a substituent containing a quaternized nitrogen atom and An ^{- is} a physiologically acceptable anion. Agent according to one of Claims 1 to 3, characterized in that the substituent containing a quaternized nitrogen atom is an N, N, N-tri- (C ₁ to C ₆ ) -alkylammonio (C ₁ to C ₆ ) - alkyl group, an N, N, N-tri (C ₁ to C ₆ ) alkylammonio (C ₂ to C ₆ ) alkoxy group, an ω- (pyridinium-1-yl) - (C ₁ to C ₆ ) - alkyl group, an ω- (pyridinium-1-yl) - (C ₁ to C ₆ ) alkoxy group, an ω- (pyrimidinium-1-yl) - (C ₁ to C ₆ ) -alkyl group, an ω- (pyrimidinium) 1-yl) - (C ₁ to C ₆ ) -alkoxy group, a ω- (3- (C ₁ to C ₆ ) -alkylimidazolium-1-yl) - (C ₁ to C ₆ ) -alkyl group, an ω- ( 3- (C ₁ to C ₆ ) -alkylimidazolium-1-yl) - (C ₁ to C ₆ ) alkoxy group, an ω- (3- (C ₁ to C ₆ ) -hydroxyalkylimidazolium-1-yl) - (C ₁ to C ₆ ) alkyl group or a ω- (3- (C ₁ to C ₆ ) -hydroxyalkylimidazolium-1-yl) - (C ₂ to C ₆ ) alkoxy group. Agent according to one of Claims 1 to 3, characterized in that the substituent containing a quaternized nitrogen atom is a substituent of the formulas (S-1) to (S-6)

wherein each n represents an integer of 1 to 6. Agent according to one of claims 1 to 5, characterized in that the substituent containing a quaternized nitrogen atom is a trimethylammonium (C ₂ -C ₆ ) alkyl group or a trimethylammonium (C ₂ -C ₆ ) alkoxy group. Agent according to one of claims 1 to 6, characterized in that it contains at least one of the following compounds as cationic organic compound of formula (I) and / or their enol form: salts of N, N, N-trimethyl-2 - [(3 oxo-2,3-dihydro-1-benzofuran-6-yl) oxy] ethanammonium, salts of N, N, N-trimethyl-3 - [(3-oxo-2,3-dihydro-1-benzofuran-6- yl) oxy] propane-1-ammonium, salts of 1- {2 - [(3-oxo-2,3-dihydro-1-benzofuran-6-yl) oxy] ethyl} pyridinium, salts of 1- {3 - [(3-oxo-2,3-dihydro-1-benzofuran-6-yl) oxy] propyl} pyridinium, salts of 3-methyl-1- {2 - [(3-oxo-2, 3-dihydro-1-benzofuran-6-yl) oxy] ethyl} -1H-imidazolium, salts of 3-methyl-1- {3 - [(3-oxo-2,3-dihydro-1-benzofuran-6- yl) oxy] propyl} -1H-imidazoliums, where the respective salts contain the physiologically acceptable anion An ^- . Agent according to one of claims 1 to 7, characterized in that the physiologically acceptable anion An ^{- is} selected from halide, 0.5 sulfate, hydrogen sulfate, 0.5 carbonate, bicarbonate, 1/3 phosphate, 0.5 hydrogen phosphate, p-toluenesulfonate, methyl sulfonate, trifluoromethanesulfonate, Benzenesulfonate, dihydrogen phosphate or carboxylate. Agent according to one of claims 1 to 8, characterized that it additionally contains at least one reactive carbonyl compound as component B. Agent according to Claim 9, characterized in that the compounds of component B are selected from compounds of the formula (B-1),

wherein • R ^1, R ² and R ³ are independently a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a hydroxy group, a C ₁ -C ₆ alkoxy group, a C ₁ -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 -C ₆ hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a Sulfonic acid group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group, an acetyl group or a nitro group, • Z 'represents 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. Agent according to one of claims 9 or 10, characterized in that the compounds of component B are selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy 1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3 Bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino 2-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4 -hydro xy-2,6-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-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3, 6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4- Dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-Dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydrox benzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydro xy-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-dodecarbaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4- hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1 naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3, 4-Dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3-hydroxy-4-nitroben aldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-one methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4- hydroxybenzaldehyde, 3-allyl-4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3.5- Diallyl-4-hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde ) and piperonal. Agent according to one of claims 1 to 11, characterized that in addition as Component C contain at least one further CH-acidic compound is different from the compounds according to formula (I). Agent according to claim 12, characterized in that that the CH-acidic compounds of component C are selected from the group consisting of physiologically compatible anions Salts of 1,4-dimethylquinolinium, 1-ethyl-4-methylquinolinium, 1-ethyl-2-methylquinolinium, 1,2,3,3-tetramethyl-3H-indolium, 2,3-dimethyl-benzothiazoliums, 2,3-dimethyl-naphtho [1,2-d] thiazolium, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium, 3-ethyl-2-methyl-benzoxazolium, 1,2,3-trimethylquinoxaluminum, 3-ethyl-2-methylbenzothiazolium, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums, 1,2-dihydro-4,6-dimethyl-1,3-dipropyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium, 1,2-Dihydro-1,3,4,5,6-pentamethyl-2-oxo-pyrimidiniums, 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-dihydro-1- (2-hydroxyethyl) -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-thiadiazolium, 1,2-dimethylquinolinium and 1,3,3-trimethyl-2-methyleneindoline (Fischer's base), oxindole, 3-methyl-1-phenyl-pyrazolin-5-one, Indan-1,2-dione, indan-1,3-dione, indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2- (2-furanoyl) acetonitrile, 2- (2-theonyl) acetonitrile, 2- (cyanomethyl) benzimidazole, 2- (cyanomethyl) benzothiazole and 2- (2,5-dimethyl-3-furanoyl) acetonitrile. Agent according to one of claims 1 to 13, characterized that the Compounds of formula I in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, are included. Agent according to one of claims 1 to 14, characterized that the Compounds of component B in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, are included. Agent according to one of claims 12 to 15, characterized that the Compounds of component C each in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant are included. Agent according to one of claims 1 to 16, characterized that it additionally as oxidation dye precursor at least one developer component and optionally at least one coupler component. Agent according to one of claims 1 to 17, characterized that it additionally at least one substantive dye, preferably in one Amount of from 0.01 to 20% by weight, based on the total colorant, contains. Agent according to one of claims 1 to 18, characterized that it additionally contains anionic, zwitterionic or nonionic surfactants. Use of at least one compound according to formula I according to claim 1 as a coloring component in hair dyes. Dyeing process keratin-containing fibers, in particular human hair, in which a colorant, according to one the claims 1 to 19, as well as usual cosmetic ingredients applied to keratin fibers, some time, usually About 15-30 minutes, left on the fiber and then again rinsed or washed out with a shampoo. Method according to claim 21, characterized in that in a two-step process, the component B according to claim 9 before or after Application of the compound according to formula I according to claim 1 applied to the keratinous fibers obtained on the hair Mix some time, usually approx. 15-30 minutes, left on the fiber and then again rinsed or washed out with a shampoo. Method according to one of claims 21 or 22, characterized that the keratin-containing fibers before a colorant according to a the claims 1 to 19 is used as part of a pretreatment with a bleaching agent bleached or with an oxidation dye colored were. Use of at least one compound according to formula I according to claim 1 for the nuancing of oxidation dyeings of keratin-containing Fibers, in particular human hair. Use of at least one compound according to formula I according to claim 1 for the color refreshment of keratin-containing dyed with oxidative colorants Fibers. Compounds according to formula (I) or their enol form

in which three of the radicals R 1, R 2, R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfonamido group, a (C ₁ -C ₆ ) -alkyl group, a ( C ₁ -C ₆ ) alkoxy group, a (C ₂ -C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) -Hydroxyalkyloxy group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II are independently is a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -alkenyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ^I and R ^II together with the nitrogen atom are 5-, 6- or 7-membered ring and m is a number 0, 1, 2, 3, 4, 5 or 6, a radical of R1, R2 R3 or R4 is a substituent containing a quaternized Nitrogen atom, X is an oxygen atom, a sulfur atom or a group NR 5, in which R 5 is a hydrogen atom, a (C ₁ -C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -alkenyl group, an aryl- (C ₁ -) C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₁ -C ₆ ) -alkoxy (C ₂ -C ₆ ) -alkyl group or a (C ₂ -C ₆ ) -polyhydroxyalkyl group and • An ^{- stands} for a physiologically compatible anion.