EP1432394A1

EP1432394A1 - Agent for coloring keratin fibers

Info

Publication number: EP1432394A1
Application number: EP02800572A
Authority: EP
Inventors: Hinrich Möller; Doris Oberkobusch; Horst Höffkes
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-10-04
Filing date: 2002-09-25
Publication date: 2004-06-30
Also published as: WO2003030846A1; DE10148842A1

Abstract

The invention relates to an agent for coloring keratin fibers, particularly human hair, containing at least one compound of formula (I), in which: R<1> represents a hydrogen atom, a C1-4 alkyl group, an aryl group or heteroaryl group; R<2>, R<3>, R<4> and R<5>, independent of one another, represent a hydrogen atom, a halogen atom, a C1-4 alkyl group, C1-4 alkoxy group or hydroxy-C1-4-alkoxy group, a hydroxy group, a nitro group, amino group, which can be substituted by C1-4 alkyl groups, or a C1-4 acyl group, whereby, together, two radicals at a time optionally form one or two condensed aromatic rings or one of the above-mentioned radicals, together with R<1>, can form part of a 5-, 6- or 7-ring; R<6> represents a C1-4 alkyl group, an aryl group, aryl-C1-4-alkyl group or heteroaryl group; R<7> and R<8>, independent of one another, represent a C1-4 alkyl group, an aryl group, aryl-C1-4-alkyl group or, together with group -OC(R<1>)(X)O-, form a 5-, 6- or 7-ring; X represents a direct bond, an optionally substituted vinylene group, methylene group or phenylene group, whereby X can also be located on a condensed aromatic ring, and; Y represents benzene sulfonate, p-toluene sulfonate, methane sulfonate, ethane sulfonate, propane sulfonate, perchlorate, sulfate, hydrogen sulfate, chloride, bromide, iodide, tetrachlorozincate, methyl sulfate, trifluoromethane sulfonate, hexafluorophosphate or tetrafluoroborate.

Description

"Means for dyeing keratin fibers"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains acetals and / or ketals, which are each derived from onium aldehydes or ketones, to the use of these compounds as a coloring component in oxidation hair dye compositions and to a process for dyeing fibers containing keratin, especially human hair.

For dyeing keratin fibers, e.g. B. hair, wool or fur, generally either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are used. Coupler and developer components are also referred to as oxidation dye precursors.

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

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

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used as coupler components. Particularly suitable coupler substances are α-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, p-phenylenediamine, 2,4-diaminophenoxyethanol , 2-Amino-4- (2'-hydroxyethylamino) anisole (Lehmanns Blau), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-di- chloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

With regard to further customary dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Culnan, H. Maibach, publisher Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248 - 250 (direct dyes), 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 disk form from the Federal Association of German Industrial and Commercial Enterprises for Medicines, Health Care Products and Personal Care Products, Mannheim ,

With oxidation dyes intensive dyeings with good fastness properties can be achieved, but the development of the color is usually done under the influence of oxidizing agents such. B. H ₂ O ₂ , which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.

The object of the present invention is to provide compounds which are suitable for dyeing keratin fibers, in particular human hair, which are qualitatively at least equivalent in terms of color depth, gray coverage and fastness properties to the customary oxidation hair dyes, but without necessarily relying on oxidizing agents such as e.g. B. H ₂ O _{2 to be} instructed. In addition, the colorants may have no or only a very low sensitization potential.

Surprisingly, it has now been found that the compounds of the formula I are outstandingly suitable for dyeing keratin-containing fibers even in the absence of oxidizing agents. They result in colors with excellent brilliance and depth of color and lead to a wide range of shades. However, the use of oxidizing agents should not be excluded in principle. The present invention relates to an agent for coloring keratin-containing

Fibers, in particular human hair, containing at least one compound of the formula I,

in the

R ¹ stands for a hydrogen atom, a C 1-4 alkyl, an aryl or heteroaryl group,

• R ² , R ³ , R ⁴ and R ⁵ independently of one another represent a hydrogen atom, a halogen atom, a a Hydroxygπ pe, a nitro group, amino group, which can be substituted by C _1- alkyl groups, or a C _1-4 acyl group, where optionally two of the radicals together form one or two fused aromatic rings or one of the above-mentioned radicals together with R ^{1 can be} part of a 5-, 6- or 7-ring,

R ⁶ represents a C _1- alkyl, an aryl, aryl-C _1-4 alkyl or heteroaryl group,

• R ⁷ and R ⁸ independently of one another form an aryl, aryl- C 1-4 alkyl group or together with the group -OC (R) (X) O- a 5-, 6- or 7-ring,

• X stands for a direct bond, an optionally substituted vinylene, methylene or phenylene group, where X can also be on a fused aromatic ring, and

• Y ^" stands for benzenesulfonate, p-toluenesulfonate, methanesulfonate, ethanesulfonate, propanesulfonate, perchlorate, sulfate, hydrogen sulfate, chloride, bromide, iodide, tetrachlorozincate, methyl sulfate, trifluoromethanesulfonate, hexafluorophosphate or tetrafluoroborate.

Examples of the C _1-4 alkyl radicals mentioned as substituents in the context of this application are the groups methyl, ethyl, propyl, / so-propyl, butyl, sec-butyl and tert- Butyl. Ethyl and methyl are preferred alkyl radicals. Preferred C _M alkoxy radicals according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C _1-4 hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A preferred hydroxy-C _1- alkoxy group is the 2-hydroxyethoxy group. A preferred C _1-4 acyl group is a formyl, an acetyl, a propionyl or a butyryl group. An example of a preferred one is an optionally substituted benzyl group. Preferred aryl groups are phenyl, naphthyl and biphenyl; a phenyl group is most preferred. Examples of halogen atoms are F, CI or Br atoms, with Cl atoms being very particularly preferred. According to the invention, the other terms used are derived from the definitions given here.

Keratin-containing fibers are wool, furs, feathers and in particular human hair. In principle, however, the colorants according to the invention can also be used for dyeing other natural fibers, such as, for. As cotton, jute, sisal, linen or silk modified natural fibers, such as. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as. B. polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.

The compounds of the formula I can be prepared from onium aldehydes or ketones and the corresponding hydroxy compounds with the help of proton catalysis with elimination of water under reaction conditions which are known to the person skilled in the art.

The compounds of the formula I are preferably selected from 2-dimethoxymethyl-1-methylpyridinium-, 3-dimethoxymethyl-1-methylpyridinium-, 4- 4- dimethoxymethyl-1-methylpyridinium-, 4- (1 ', 3'-dioxolan-2 '-yl) -1-methylpyridinium-, 1-methyl-4- (4'-methyl-1', 3'-dioxolan-2'-yl) -pyridinium-, 2-diethoxymethyl-1-ethylpyridinium-, 3- Diethoxymethyl-1-ethylpyridinium-, 4-diethoxymethyl-1 -ethylpyridinium-, 2-

Dimethoxymethyl-1-benzylpyridinium-, 4-dimethoxymethyl-1 -benzylpyridinium-, 4-dimethoxymethyl-1, 2-dimethylpyridinium-, 4-dimethoxymethyl-1, 3-dimethylpyridinium-, 2-dimethoxymethyl-1-methylquinolinoxym, 4-dimethoxymethyl -1-methylquinolinium--, 5- dimethoxymethyl-1-methylquinolinium-, 7-dimethoxymethyl-1-methylquinolinium-, 2- Diethoxymethyl-1-methylquinolinium-, 4-diethoxymethyl-1-methylquinolinium-, 5-diethoxymethyl-1-methylquinolinium-, 7-diethoxymethyl-1-methylquinolinium-, 4- (2 ', 2'-dimethoxyethyl) -1-methylpyridinium- , 2- (2 ', 2'-dimethoxyethyl) -1-methylpyridinium-, 2- (2', 2'-dimethoxyethyl) -1-methylquinolinium-, 4- (α, α-dimethoxybenzyl) -1 - methylpyridinium-, 4- (2 '- (Diethoxymethyl) vinyl) -1-methylpyridinium-, 9-

Dimethoxymethylacridinium, 9,9-dimethoxy-1-methylindeno [2,1-b] pyridinium salts, in particular the benzenesulfonates, p-toluenesulfonates, methanesulfonates, ethanesulfonates, propanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides, tetrachlorozincates, methyl sulfates , Trifluoromethanesulfonates, hexafluorophosphates, tetrafluoroborates and any mixtures thereof.

The abovementioned compounds having the formula I are preferably used in the agents according to the invention in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the entire colorant. They can be used as substantive colorants or in the presence of customary oxidation dye precursors.

Coloring agents which contain compounds of the formula I as the coloring component are preferably used for lighter colors. Colorings with even greater brilliance and improved fastness properties (light fastness, wash fastness, rub fastness) over a range of shades from yellow to yellow-brown, orange, brown-orange, medium brown, dark brown, violet, dark violet to blue-black and black are achieved if the compounds used according to the invention with the Formula I together with at least one further component (hereinafter referred to as component B), selected from compounds having a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, built up from 2 to 9 amino acids Oligopeptides and / or CH-acidic compounds can be used. On the one hand, these are compounds which, on their own, only weakly dye keratin-containing fibers and only give brilliant colors together with the compounds of the formula I. On the other hand, there are also compounds that are already used as oxidation dye precursors. Several compounds of the formula I can also be used together in all colorants; Likewise, several different compounds of component B can also be used together.

The embodiment described above also includes the use of those substances which are reaction products of compounds of the formula I with the compounds of component B mentioned, as substantive colorants. Such reaction products can e.g. B. be obtained by briefly heating the two components in stoichiometric amounts in an aqueous neutral to weakly alkaline medium, they either precipitate out of the solution as a solid or are isolated therefrom by evaporation of the solution. The reaction products can also be used in combination with other dyes or dye precursors.

Suitable compounds with primary or secondary amino group as component B are e.g. B. primary aromatic amines such as N, N-dimethyl-, N, N-diethyl-, N- (2'-hydroxyethyl) -N-ethyl-, N, N-bis- (2'-hydroxyethyl) -, N- (2'-methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline dihydro- bromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenol, - phenethole , 4-amino-3-methylphenol, 2- (2 ', 5'-diaminophenyl) -ethanol, 2,4-diaminophen-oxyethanol, 2- (2', 5'-diaminophenoxy) -ethanol, 4-methylamino, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl -5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2'-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5-amino- 4-chloro-, 3,4-methylenedioxy-, 5- (2'-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-hydroxymethylphenol, 1, 3-diamino-2,4- dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2, 3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxy-benzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene 2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-, 1, 2,4-triaminobenzene, 1 , 2,4,5-tetraaminobenzene, 2,4,5-thaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobenzate catechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxybrenzcatechin . aromatic cyano group and / or nitro group-containing amino compounds, such as 3-amino-6-methylamino-2-nitro-pyridine, picraminic acid, [8 - [(4'-amino-2'-nitrophenyl) azo] -7-hydroxy- 2-naphthyl] trimethylammonium chloride, [8 - [(4'-amino-3'-nitrophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6 -Dinitro-benzene, 1-amino-2-nitro-4-bis- (2'-hydroxyethyl) -amino-benzene, 1-amino-2- (2'-hydroxyethyl) -amino-5-nitro-benzene (HC Yellow No. 5), 1-amino-2-nitro-4- (2'-hydroxyethyl) aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1, 4-phenylenediamine, 1- (2-hydroxyethyl) amino-2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine , 1-amino-3-methyl-4- (2'-hydroxyethyl) amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- (2 ', 3'-dihydroxypropyl) -amino-5-chlorobenzene (HC Red No. 10), 4-amino-2-nitrodiphenylamino-2'-carboxylic acid (2- (4'-amino-2'-nitroanilino) -benzoic acid), 6-nitro- 2,5-diaminopyri din, 2-amino-6-chloro-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3'-nitrophenylazo) -7-phenylazo-8-naphthol-3,6 disulfonic acid, disodium salt (Acid blue No. 29), 1-amino-2- (2'-hydroxy-4'-nitrophenylazo) -8-naphthol-3,6-disulfonic acid,

Disodium salt (palatinchrome green), 1-amino-2- (3'-chloro-2'-hydroxy-5'-nitrophenylazo) - 8-naphthol-3,6-disulfonic acid disodium salt (gallion), 4-amino-4'- nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2 -sulfonic acid, 4'-amino-3'-nitro-benzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2'-nitrobenzylidenamino) benzene, 2- [2'- (diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid (hydrate), 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5 -Amino-6-nitrobenzo-1, 3-dioxole, anilines, especially nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1, 4-diamino-2-nitrobenzene, 1, 2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1 - (2'-hydroxyethylamino) benzene, 2-nitro-1-amino-4 - [bis- (2'-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2'-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as described in formula II are shown

in the

R ^{9 represents} a hydroxyl or an amino group which may be substituted by C _1-4 alkyl, C ₁ -hydroxyalkyl, d_ ₄ -alkoxy or C _1-4 alkoxy-C ₁ -alkyl groups,

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently of one another represent hydrogen, a hydroxyl or an amino group which can be substituted by C _1-4 alkyl, C _1- - aminoalkyl or can be substituted, stand, and

• Q for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms, optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula III

Z- (CH ₂ -P-CH ₂ -Z ') ₀ (IM)

in the

P denotes a direct bond, a CH ₂ or CHOH group,

Z and Z 'independently of one another for an oxygen atom, an NR ¹⁵ group, in which R ^{15 is} hydrogen, a C _1-4 -alkyl or a hydroxy-d ^ -alkyl group, the group O- (CH ₂ ) _p - NH or NH- (CH ₂ ) _p '-O, where p and p' are 2 or 3, and

A number from 1 to 4 means

such as 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4, 4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl , 3,3 ', 4,4'-tetraamino-benzophenone, 1, 3-bis (2', 4'-diaminophenoxy) propane, 1, 8-bis (2 ', 5'-diaminophenoxy) -3 , 6-dioxaoctane, 1,3-bis- (4'-aminophenylamino) propane, -2-propanol, 1,3-bis- [N- (4'-aminophenyl) -2-hydroxyethylamino] -2-propanol, N , N-bis- [2- (4'-aminophenoxy) ethyl] methylamine, N-phenyl-1,4-phenylenediamine.

The abovementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid. Suitable nitrogen-containing heterocyclic compounds are e.g. B. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino -, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamine-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino, 4,5,6-triamino, 4-hydroxy-2,5,6-triamino, 2-hydroxy -4,5,6-triamino-, 2,4,5, 6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2- Amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8- Aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. According to the invention, the hydroxypyrimidines disclosed in DE-U1-299 08 573 can also be used as heterocyclic compounds. The aforementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, e.g. B. as salts of inorganic acids such as hydrochloric or sulfuric acid.

Suitable aromatic hydroxy compounds are e.g. B. 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino -, 2- (2'-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7- naphthalenedisulfonic.

Preferred amino acids are all naturally occurring and synthetic α-amino acids, e.g. obtained by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids can be used. Preferred amino acids are proline, tyrosine, arginine, histidine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. But also other amino acids, e.g. 6-aminocaproic acid and β-alanine can be used.

The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, so if they have sufficient water solubility for use in the colorants of the invention. Examples include glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is preferred.

Examples of suitable CH-acidic compounds are 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3,3-tetramethyl - 3H-indolium methanesulfonate, 1, 3,3-trimethyl-2-methyleneindoline (Fischer's base), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, 1, 2-dimethyl -naphtho [1,2-d] thiazolium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-methyl -2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, 1, 3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindoleic acid -Indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone, 1, 4-dimethylquinolinium, 1, 2-dimethylquinolinium, 1, 4-dimethylpyridinium, 1, 2-dimethylpyridinium, 2,4,6 -Trimethylpyrilium-, 2-methyl-1-ethylquinolinium-, 2,3-dimethyl-isoquinolinium-, 1, 2,3,3 -Tetramethyl-3H-indolium-, 2,3-dimethylbenzothiazolium-, 2,3-dimethyl-6-nitrobenzothiazolium-, 3-benzyl-2-benzothiazolium-, 2-methyl-3-propylbenzothiazolium-, 2,4-dimethyl- 3-ethylthiazolium-, 3- (2'-carboxyethyl) -2,5-dimethylbenzothiazolium-, 1, 2,3-trimethylbenzimidazolium-, 5,6-dichloro-1, 3-diethyl-2-methylbenzimidazolium-, 3-ethyl -2-methylbenzothiazolium, 3-ethyl-2-methylnaphtho [1, 2-d] thiazolium, 5-chloro-3-ethyl-2-methylbenzothiazolium, 3-ethyl-2-methylbenzoxazolium salts, e.g. B. as chlorides, bromides, iodides, methanesulfonates, benzenesulfonates, p-toluenesulfonates, trifluoromethanesulfonates, methyl sulfates, tetrafluoroborates, and 2-methyl-3- (3'-sulfopropyl) benzothiazolium hydroxide (inner salt), 4-methyl -1- (3'-sulfopropyl) pyridinium hydroxide (inner salt), 4-methyl-1- (3'-sulfopropyl) quinolinium hydroxide (inner salt), 5-methoxy-2-methyl-3- ( 3'-sulfopropyl) benzothiazolium hydroxide (inner salt), 1-methyl-3-phenylpyrazolinone, indane-1,3-dione, cyclopentane-1,3-dione, 1,2-dihydro-1-ethyl-6- hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile, 1-dicyanomethylene indane, 1-dicyanomethylene indan-3-one, 4 - [(1-methyl- 4 (1 H) -pyridinylidene) ethylidene] -2,5- cyclohexadien-1-one, 4- (4'-hydroxystyryl) -1-pyridinium-3-propyl sulfonate, 2- (4'-hydroxystyryl) -1-methylpyridinium iodide, 4- (4'-methoxysty- ryl) -1-methylpyridinium iodide, 2- (4'-methoxystyryl) -1-methylpyridinium iodide, 1 -ethyl-2- (4'- hydroxystyryl) pyridinium iodide, 1-methyl-4- (3 ', 4'-methylenedioxystyryl) pyridinium iodide, 2- (4'-ethoxystyryl) -1-methylpyridinium iodide, 1-ethyl-2- (4 '-methoxystyryl) -pyridinium iodide, 1-methyl-2- (4'-hydroxy-3'-methoxystyryl) -pyridinium-iodide, 1-ethyl-2- (3', 4'-methylenedioxy-styryl) -pyhdinium -iodide, 1-ethyl-4- (3 ', 4'-methylenedioxystyryl) -quinolinium iodide, 4- (3', 4'-dimethoxystyryl) -1-methylquinolinium iodide, 1-ethyl-4- ( 4'-hydroxystyryl) quinolinium iodide, 1-ethyl-2- (4'-hydroxystyryl) quinolinium iodide and any mixtures of the foregoing.

The compounds of component B are particularly preferably selected from the group consisting of N- (2'-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis- (2'-hydroxyethyl) -p -phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2 ', 5'-diamino-phenyl) -ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2'-hydroxyethyl - amino) anisole, 2- (2 ', 4'-diaminophenoxy) ethanol, 3-amino-2,4-dichloro, 2-methyl-5-amino, 3-methyl-4-amino, 2 -Methyl-5- (2'-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl - 4-aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,6- Dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-met hylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, ß-alanine, L-proline, L-lysine, DL-tyrosine and their physiologically tolerable salts formed with preferably inorganic acids.

The above-mentioned compounds of component B can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the entire colorant. Furthermore, it can be particularly preferred according to the invention to use the compound of formula I and the compound of component B in a molar ratio of 2: 1 to 1: 4, in particular approximately equimolar. When using compounds of component B which contain two or more amino groups, the compounds of formula I on the one hand and the compounds of component B on the other hand can also be used in stoichiometric proportions.

To obtain further and more intense colorations, the inventive Means additionally contain color enhancers. The color enhancers are preferably selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, Histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine, their derivatives and their physiologically tolerable salts.

The aforementioned color enhancers can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the entire colorant.

On the presence of oxidizing agents, e.g. B. H ₂ O ₂ , can be omitted. However, it can It may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve the shades which are lighter than the keratin-containing fiber to be colored. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

In a preferred embodiment, the colorants according to the invention contain, in addition to the compounds contained according to the invention, customary direct dyes, for example, for further modification of the color shades. B. from the group of nitro-phenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as. B. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine - 2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1, 4-bis- (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl -3-nitro-4- (2'-hydroxyethyl) aminobenzene. The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes, such as those in, for example, henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root are included.

It is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

The colorants according to the invention produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants can usually be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming solutions such. B. shampoos or other preparations that are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the colorants into anhydrous carriers.

Furthermore, the colorants according to the invention can contain all active ingredients, additives and auxiliaries known in such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are in each case in the form the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon 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 with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 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 with 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 hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 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, the addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 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 surface-active compounds that contain at least one quaternary ammonium group and at least one in the molecule -COO * ^" 'or -SOs ^ group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ -is alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule 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 with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

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

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

Atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,

Cι ₂ . ₂₂ fatty acid monoesters and diesters of adducts from 1 to 30 mol

Ethylene oxide on glycerol,

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

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

Castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters

Addition products of ethylene oxide with fatty acid alkanolamides. Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammoniumchlor.de, dialkyldimethylammonium chloride and trialkylmethylammonium chlorides, for. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the ^{stearylamidopropyldimethylamine} available under the name Tego Amid ^® S 18, are notable for their good biodegradability.

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

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

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained. In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotaicites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidoneA inylacetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary acrylate groups, dimethyl-dimethyldiallyiallyl dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonolamide / acrylate methylacrylate / acrylate. -Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone amyl acrylate copolymers, Vinyla acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol, structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

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

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

Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, 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, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

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

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; z. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are e.g. 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, 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 present in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant.

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

The present invention further relates to the use of compounds of the formula I

in which R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , X and Y ^"are as defined above as a coloring component in oxidation hair colorants.

The present invention further relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant comprising A) at least one compound of the formula I,

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X and Y ^"are as defined above and if necessary

B) at least one compound having a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, aromatic hydroxy compounds, amino acids, oligopeptides composed of 2 to 9 amino acids and / or at least one CH-acidic compound , and usual cosmetic ingredients, applied to the keratin fibers, left on the fibers for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.

The compounds of formula I and the compounds of component B can either be applied to the hair at the same time or else in succession, it being irrelevant which of the two components is applied first. The optionally contained ammonium or metal salts can be added to the first or the second component. There may be an interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the fibers with the saline solution is also possible.

The compounds of formula I and the compounds of component B can either be stored separately or together, either in a liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, this should be largely anhydrous to reduce a reaction of the components. When stored separately, the reactive components are only intimately mixed with one another immediately before use. In dry storage, a defined amount of warm (30 to 80 ° C) water is usually added before use and a homogeneous mixture is produced.

The compounds are new and therefore a further subject of the present invention:

4-diethoxymethyl-1-methylquinolinium p-toluenesulfonate, 4-dimethoxymethyl-1-methylquinolinium p-toluenesulfonate, 2-diethoxymethyl-1-methylquinolinium p-toluenesulfonate and 2-dimethoxymethyl-1-methylquinolinium p-toluenes. Examples

Preparation Examples

4-diethoxymethyl-1-methylquinolinium-p-toluenesulfonate

The stirred mixture of 17.2 g (0.05 mol) of 4-formyl-1-methylquinolinium p-toluenesulfonate, 37 g (0.25 mol) of triethyl orthoformate, 7.5 ml (0.15 mol) of ethanol and 5 drops Trifluoroacetic acid was heated to boiling under reflux for 8 hours. The clear solution obtained was completely evaporated in a rotary evaporator and the crystalline product was pressed onto clay plates and dried in a desiccator. 16.9 g (81% of theory) of 4-diethoxymethyl-1-methylquinolinium p-toluenesulfonate with a melting point of 65-68 ^° C. were obtained.

The following acetals were synthesized analogously:

4-Dimethoxymethyl-1-methylquinolinium p-toluenesulfonate: mp 120-125 ° C 2-diethoxymethyl-1-methylquinolinium p-toluenesulfonate: mp 60-65 ° C 2-dimethoxymethyl-1-methylquinolinium p-toluenesulfonate: Mp 115-120 ° C

Preparation of a coloring solution

A slurry of 5 mmol of onium acetal of the formula I and optionally of 5 mmol of a compound according to component B, each with 5 mmol of sodium acetate and a drop of a 20% strength fatty alkyl ether sulfate solution in 50 ml of water at 50 ° C., was prepared. The slurries of the onium acetal and the compound of the formula I were mixed with one another after cooling to 30 ° C. and adjusted to a pH of 6 with dilute NaOH or hydrochloric acid.

A strand of 90% gray, untreated human hair was introduced into this dye mixture at 30 ° C. for 30 minutes. The tress was then rinsed with lukewarm water for 30 seconds, dried with warm air and then combed out.

The respective color shades and color depths are shown in the following tables. The color depth was rated on the following scale:

no or very pale color

(+) weak intensity

+ medium intensity

+ (+) medium to strong intensity ++ strong intensity

++ (+) strong to very strong intensity

+++ very strong intensity

Table 1

Ausfärbunqen with 4-diethoxymethyl-1-methyl-quinolinium-p-toluenesulfonate

Table 2

Ausfärbunqen with 4-dimethoxymethyl-1-methyl-quinolinium-p-toluenesulfonate

Table 3

Ausfärbunqen with 2-diethoxymethyl-1-methyl-quinolinium-p-toluenesulfonate

Table 4

Ausfärbunqen with 2-dimethoxymethyl-1-methyl-quinolinium-p-toluenesulfonate

Claims

claims

1. agent for dyeing keratin fibers, in particular human hair, containing at least one compound of the formula I,

in the

R ¹ represents a hydrogen atom, a C alkyl group, an aryl or heteroaryl group,

R ² , R ³ , R ⁴ and R ⁵ independently of one another represent a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C ₄ alkoxy or hydroxyC _1-4 alkoxy group, a hydroxy group, a nitro group, amino group, which can be substituted by C _1-4 alkyl groups, or a C _1-4 acyl group, where in each case two of the radicals together form one or two fused aromatic rings or one of the above radicals together with R ¹ Can be part of a 5-, 6- or 7-ring,

R ⁶ represents a C 1-4 alkyl, an aryl, aryl-C 1-4 alkyl or heteroaryl group,

R ⁷ and R ⁸ independently of one another represent ad ^ -alkyl, an aryl, aralkyl group or together with the group -OC (R) (X) O- form a 5-, 6- or 7-ring,

2. Composition according to claim 1, characterized in that as compounds with the formula I 2-dimethoxymethyl-1-methylpyridinium-, 3-dimethoxymethyl-1- methylpyridinium-, 4-dimethoxymethyl-1-methylpyridinium-, 4- (1 ', 3'-dioxolan-2'-yl) - 1 -methylpyridinium-, 1-methyl-4- (4'-methyl-1', 3 '-dioxolan-2'-yl) -pyridinium-, 2-diethoxymethyl-1 -ethylpyridinium-, 3-diethoxymethyl-1 -ethylpyridinium-, 4-

Diethoxymethyl-1-ethylpyridinium-, 2-dimethoxymethyl-1 -benzylpyridinium-, 4-dimethoxymethyl-1 -benzylpyridinium-, 4-dimethoxymethyl-1, 2-dimethylpyridinium-, 4-dimethoxymethyl-1, 3-dimethylpyridinium-, 2-dimethoxym -1-methylquinolinium-, 4-dimethoxymethyl-1-methylquinolinium-, 5-dimethoxymethyl-1 - methylquinolinium-, 7-dimethoxymethyl-1-methylquinolinium-, 2-diethoxymethyl-1 - methylquinolinium-, 4-diethoxymethyl-1-methylquinolinium- , 5-diethoxymethyl-1 - methylquinolinium-, 7-diethoxymethyl-1-methylquinolinium-, 4- (2 ', 2'-dimethoxyethyl) - 1-methylpyridinium-, 2- (2', 2'-dimethoxyethyl) -1 - methylpyridinium-, 2- (2 ', 2'-

Dimethoxyethyl) -1-methylquinolinium-, 4- (α, α-dimethoxybenzyl) -1-methylpyridinium-, 4- (2- (diethoxymethyl) -vinyl) -1-methylpyridinium-, 9-dimethoxymethylacridinium-, 9,9-dimethoxy -1-methylindeno [2, 1 -pjpyridinium salts, especially the

Benzenesulfonates, p-toluenesulfonates, methanesulfonates, ethanesulfonates,

Propanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides, tetrachlorozincates, methyl sulfates, trifluoromethanesulfonates, hexafluorophosphates, tetrafluoroborates and any mixtures thereof are contained.

3. Composition according to claim 1 or 2, characterized in 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 contained.

4. Composition according to one of claims 1 to 3, characterized in that there is additionally at least one further compound having a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, from 2 to 9 Contains amino acid oligopeptides and / or at least one CH-acidic compound.

5. Composition according to claim 4, characterized in that the further compound is selected from primary or secondary amines from the group consisting of N- (2'-hydroxyethyl) -N-ethyl-, N- (2'-methoxyethyl -), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2- Chloro-p-phenylenediamine, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2,5-

Dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2 ', 5'-diaminophenyl) ethanol, 2, 5- diaminotoluene, phenol, phenethole, 4-methylamino, 3-amino-4- (2'-hydroxyethyloxy) - 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro -, 4-methylamino, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2'-hydroxyethylamino) -, 2-methyl-5-amino-4 -chloro, 6-methyl-3-amino-2-chloro, 5- (2'-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-aminomethylphenol, 2-hydroxymethyl-4 -aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethyl-aminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 1, 3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4 -Aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4- Amino-3-hydroxy-benzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalenesulfonic acid, 6-Am ino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-A-mino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-amino- phthalic acid, 5-aminoisophthalic acid, 1, 3,5-, 1, 2,4-triaminobenzene, 1, 2,4,5-tetraaminobenzene-tetrahydrochloride, 2,4,5-triaminophenol-trihydrochloride, penta-aminobenzene-pentahydrochloride , Hexaaminobenzene hexahydrochloride, 2,4,6-Triaminoresorcin trihydrochloride, 4,5-Diaminobrenzcatechinsulfat, 4,6-Diaminopyrogallol dihydrochloride, 3,5-Diamino-4-hydroxybrenzcatechin sulfate, aromatic

Amine compounds containing cyano groups and / or nitro groups, such as 3-amino-6-methylamino-2-nitro-pyridine, picraminic acid, [8 - [(4'-amino-2'-nitrophenyl) azo] -7-hydroxy-2 -naphthyl] trimethylammonium chloride, [8 - [(4'-amino-3'-nitrophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6- dinitro-benzene, 1-amino-2-nitro-4-bis- (2'-hydroxyethyl) amino-benzene, 1-amino-2- (2'-hydroxyethyl) amino-5-nitro-benzene (HC Yellow No. 5), 1-amino-2-nitro-4- (2'-hydroxyethyl) aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1,4-phenylenediamine, 1 - (2'-Hydroxyethyl) amino-2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine , 1-Amino-3-methyl-4- (2'-hydroxyethyl) amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- (2 ', 3'-dihydroxypropyl) -amino-5-chlorobenzene (HC Red No. 10), 4-amino-2-nitrodiphenyl-amino-2'-carboxylic acid (2- (4'-amino-2'-nitroanilino) -benzoic acid), 6-nitro- 2,5-diaminopyridine, 2-Am ino-6-chloro-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3'-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid Disodium salt (Acid blue No. 29), 1-amino-2- (2'-hydroxy-4'-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Palatinchrome green), 1-amino-2- (3rd '- chloro-2'-hydroxy-5'-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt

(Gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4) , 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1 - amino-4-nitro-2- (2'-nitrobenzylideneamino) benzene, 2- [ 2 '- (diethylamino) ethylamino] - 5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid (hydrate), 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2- Amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1, 3-dioxole, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1, 4-diamino-2-nitrobenzene, 1, 2 Diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1 - (2'-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2'-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-Amino-5-chloro-4- (2'-hydroxyethylamino) -2-nitrobenzene, anilines, in particular containing nitro groups e anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2'-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2'-hydroxyethyl) amino] benzene, 4- Amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2'-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid sodium salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4 ' -Diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3 ', 4,4'-

Tetraaminodiphenyl tetrahydrochloride, 3,3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2', 4'-diaminophenoxy) propane tetrahydrochloride, 1,8-bis (2 ', 5' -diaminophenoxy) -3,6- dioxaoctane-tetrahydrochloride, 1,3-bis- (4'-aminophenylamino) -propane, -2-propanol, 1,3-bis- [N- (4'-aminophenyl) -2- hydroxyethylamino] -2-propanol, N, N-bis- [2- (4'-aminophenoxy) ethyl] methylamine trihydrochloride, nitrogen-containing heterocyclic compounds selected from the group consisting of 2-, 3-, 4-amino -, 2-Amino-3-hydroxy-, 2,6-diamino-, 2,5-diamino-, 2,3-diamino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6 -methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine , 4,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino -4,5,6-triamino-, 2,4-, 4,5-diamino-, 2- Amino-4-methoxy-6-methyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino -, 3-Amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino benzimidazole, benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5, 6-dihydroxyindole, 5,6-dihydroxyindoline, 4-hydroxyindoline and hydroxypyrimidine derivatives, and in each case from the physiologically tolerable salts of these compounds formed with preferably inorganic acids, aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2'-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid e, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, - acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4 -hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid,

Amino acids selected from the group ß-alanine, proline, tyrosine, arginine, histidine, phenylalanine, DOPA (dihydroxyphenylalanine), omithin, lysine and tryptophan, oligopeptide selected from glutathione or those in the hydrolysates of collagen, keratin, casein, elastin, soy protein, Oligopeptides containing wheat gluten or almond protein

CH-acidic compounds selected from 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H- indolium methanesulfonate, 1, 3,3-trimethyl-2-methyleneindoline (Fischer's base), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, 1, 2-dimethyl- naphtho [1,2-d] thiazolium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-methyl-2- quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, 1, 3-diethylthiobarbituric acid, diethylthiobarbiturate acid, oxindanonlac, oxindanol, 1-methyl-3-phenyl-2-pyrazolinone, 1, 4-dimethylquinolinium, 1, 2-dimethylquinolinium, 1, 4-dimethylpyridinium, 1, 2-dimethylpyridinium, 2,4,6-trimethylpyrilium, 2 -Methyl- 1 -ethylquinolinium-, 2,3-dimethylisoquinolinium-, 1, 2,3,3-tetramethyl-3H-indolium-, 2,3-dimethylbenzothiazolium-, 2,3-dimethyl-6-nitrobenzothiazolium-, 3-benzyl-2- benzothiazolium-, 2-methyl-3-propylbenzothiazolium-, 2,4-dimethyl-3-ethylthiazolium-, 3- (2'-carboxyethyl) -2,5-dimethylbenzothiazolium-, 1, 2,3-trimethyl-benzimidazolium-, 5,6-dichloro-1, 3-diethyl-2-methylbenzimidazolium, 3-ethyl-2-methylbenzothiazolium, 3-ethyl-2-methylnaphtho [1, 2-d] thiazolium, 5-chloro-3-ethyl - 2-methylbenzothiazolium, 3-ethyl-2-methylbenzoxazolium salts which, for. B. as chlorides, bromides, iodides, methanesulfonates, benzenesulfonates, p-toluenesulfonates, trifluoromethanesulfonates, methyl sulfates, tetrafluoroborates, and 2-methyl-3- (3'-sulfopropyl) benzothiazolium hydroxide (inner salt), 4th -Methyl-1- (3'-sulfopropyl) pyridinium hydroxide (inner salt), 4-methyl-1- (3'-sulfopropyl) quinolinium hydroxide (inner salt), 5-methoxy-2-methyl-3 - (3'-sulfopropyl) - benzothiazolium hydroxide (inner salt), 1-methyl-3-phenylpyrazolinone, indane-1,3-dione, cyclopentane-1,3-dione, 1,2-dihydro-1-ethyl 6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile, 1-dicyanomethylene indane, 1-dicyanomethylene indan-3-one, 4 - [(1-methyl-4 (1 H) -pyridinylidene) ethylidene] -2, 5-cyclohexadien-1-one, 4- (4'-hydroxystyryl) -1-pyridinium-3-propyl sulfonate, 2- (4'-hydroxystyryl) -1-methylpyridinium iodide, 4- (4'-methoxystyryl) -1-methylpyridinium iodide, 2- (4'-methoxystyryl) -1 -methylpyridinium iodide, 1 -ethyl-2- (4'-hydroxystyryl) pyridinium iodide, 1-methyl-4- (3 ', 4 '- methylenedioxystyr yl) pyridinium iodide, 2- (4'-ethoxystyryl) -1-methylpyridinium iodide, 1-ethyl-2- (4'-methoxystyryl) pyridinium iodide, 1-methyl-2- (4'-hydroxy -3'- methoxystyryl) pyridinium iodide, 1-ethyl-2- (3 ', 4'-methylenedioxystyryl) pyridinium iodide, 1-ethyl-4- (3', 4'-methylenedioxystyryl) quinolinium iodide , 4- (3 ', 4'-Dimeth-oxystyryl) -1-methylquinolinium iodide, 1-ethyl-4- (4'-hydroxystyryl) -quinolinium iodide, 1-ethyl-2- (4'-hydroxystyryl) -chinolinium iodide.

6. Composition according to one of claims 4 or 5, characterized in that the further compound is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N- Bis- (2'-Hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) -ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2 -Amino-4- (2'-hydroxyethylamino) anisole, 2- (2 ', 4'-diaminophenoxy) ethanol, 3-amino-2,4-dichloro-, 2-methyl-5-amino-, 3- Methyl-4-amino, 2-methyl-5- (2'-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-aminomethyl -4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-methylenedioxyphenol, 3,4-diaminobenzoic acid right, 2,5-diamino, 2-dimethylamino-5-amino, 3-amino-2-methylamino-6-methoxy, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino- , 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetra-amino-, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino -5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, ß-alanine, L-proline, L-lysine, DL-tyrosine and in each case from the physiologically tolerable salts of these compounds which are preferably formed with inorganic acids.

7. Composition according to one of claims 1 to 6, characterized in that there are color enhancers selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3rd -Hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine or any mixtures thereof.

8. Agent according to one of claims 1 to 7, characterized in that there are direct dyes from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant , contains.

9. Composition according to one of claims 1 to 8, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, Propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, can be added.

10. Agent according to one of claims 1 to 9, characterized in that it contains at least one oxidizing agent, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution.

11. Agent according to one of claims 1 to 10, characterized in that it contains anionic, zwitterionic or nonionic surfactants.

12. Use of compounds according to formula I,

in the

R ¹ represents a hydrogen atom, a C 1 -alkyl, an aryl or heteroaryl group,

• R ² , R ³ , R ⁴ and R ⁵ independently of one another represent a hydrogen, a halogen atom, a C _1-4 alkyl, C ^ alkoxy or hydroxy-C ^ alkoxy group, a hydroxy group, a nitro group , Amino group, which can be substituted by C 1-4 alkyl groups, or a C _1-4 -acyl group, where in each case two of the radicals together form one or two fused aromatic rings or one of the above-mentioned radicals together with R ^{1 form} part of a 5- , 6 or 7 rings can be

• R ⁶ stands for a Cι. Alkyl, an aryl, aryl-C 1-4 alkyl or heteroaryl group,

• R ⁷ and R ⁸ independently of one another represent a C ^ alkyl, an aryl, aryl, C ^ alkyl group or together with the group -OC (R ¹ ) (X) O- a 5-, 6- or Form 7-ring,

• Y ^" stands for benzenesulfonate, p-toluenesulfonate, methanesulfonate, ethanesulfonate, propanesulfonate, perchlorate, sulfate, hydrogen sulfate, chloride, bromide, iodide, tetrachlorozincate, methyl sulfate, trifluoromethanesulfonate, hexafluorophosphate or tetrafluoroborate

as a coloring component in oxidation hair dyes.

13. A method for dyeing keratin fibers, in particular human hair, in which a colorant containing A) at least one compound of the formula I.

in the

R represents a hydrogen atom, a C _1-4 alkyl, an aryl or heteroaryl group,

• R ² , R ³ , R ⁴ and R ⁵ independently of one another represent a hydrogen, a halogen atom, a C _1-4 alkyl, C _1- alkoxy or hydroxy-C _1-4 alkoxy group, a hydroxy group , a nitro group, amino group, which can be substituted by C ^ alkyl groups, or a C _1-4 acyl group, where two of the radicals together form one or two fused aromatic rings or one of the above radicals together with R part of one Can be 5-, 6- or 7-rings

R ⁶ represents a C 1-4 alkyl, an aryl, aryl-C 1-4 alkyl or heteroaryl group,

• R ⁷ and R ⁸ independently of one another an aryl, aryl, C _1-4 alkyl group or together with the group -OC (R ¹ ) (X) O- form a 5-, 6- or 7-ring,

• Y ^" stands for benzenesulfonate, p-toluenesulfonate, methanesulfonate, ethanesulfonate, propanesulfonate, perchlorate, sulfate, hydrogen sulfate, chloride, bromide, iodide, tetrachlorozincate, methyl sulfate, trifluoromethanesulfonate, hexafluorophosphate or tetrafluoroborate and optionally

B) at least one compound with a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, from 2 to 9 amino acids built oligopeptides and / or at least one CH-acidic compound, as well as usual cosmetic ingredients, applied to the keratin-containing fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.

14. 4-Diethoxymethyl-1-methylquinolinium p-toluenesulfonate.

15. 4-Dimethoxymethyl-1-methylquinolinium p-toluenesulfonate.

16 2-Diethoxymethyl-1-methylquinolinium p-toluenesulfonate.

17. 2-Dimethoxymethyl-1-methylquinolinium p-toluenesulfonate.