DE19802940C2 - New cationic dyes, processes for their preparation and dyes containing these dyes for keratin fibers - Google Patents

Description

The present invention relates to new cationic dyes, a process for their preparation, dyeing containing these dyes agent for keratin fibers, especially human hair, and a ver drive to dye hair using this dye.

For the color-changing treatment of keratin fibers, for Examples of human hair, wool or furs, are usually found two staining procedures applied. In the first procedure, the coloring with so-called oxidative or permanent colorants under Ver application of a mixture of different developer substances and Coupler substances and an oxidizing agent. If necessary to round off the coloring result or to create be special color effects so-called direct (non-oxidative) color substances are added. The second method uses only direct dyes, which are in a suitable carrier mass on the Fibers are applied. This procedure is easy to use extremely mild and is characterized by a slight damage to the Keratin fiber. To the direct dyes used here there are a variety of requirements. So you have to be in toxic logical and dermatological considerations and the education development of colorations in the desired intensity enable what is under also requires sufficient water solubility. Except This is good lightfastness, acid for the dyeings achieved  authenticity and rub fastness required. Their use in oxidation dyes also presupposes that the dyes are opposite Hydrogen peroxide in ammoniacal solution and against anti oxidants are stable.

For a direct (non-oxidative) colorant for keratin fibers is usually a combination of different non-oxidative Dyes needed. Because the selection of red and blue dyes that in colorants for keratin fibers, especially human hair can be set, there is an urgent need the expansion of the usable dye range.

There is a wide range of different ones for textile dyeing Dyes, for example disperse dyes, or solvent dyes; however, these dyes are only partially water-soluble and he give an extremely weak coloring of aqueous mixtures Keratin fibers. Therefore, the use of a significant number of Dyes for coloring keratin fibers, especially hair coloring, so far not possible.

Surprisingly, it has now been found that through the introduction tion of a cationic group into a dyes water-soluble form can be converted and thus direct Dyes are obtained which meet the above requirements largely meet.  

The present invention therefore relates to cationic dyes of the general formula (I)

where n and z are one or two and the radicals given in the formula (I) have the following meaning:
B ^{z +} is equal to a quaternary ammonium group, a quaternary phosphonium group or a sulfonium group;
Y is an unsubstituted, straight-chain or branched C ₁ to C ₆ alkylene group or a substituted, straight-chain or branched C ₂ to C ₆ alkylene group;
X is oxygen or an NR ¹ group, with R ¹ being hydrogen or a C ₁ to C ₆ alkyl radical;
R is equal to a dye radical, a suitable dye R-XH being an azo dye, a nitro dye, an anthraquinone dye, an anthocyanin, a triphendioxazine, a diphenylbenzofuran dione or a diphenylbenzopyrrole dione with at least one OH group or an NHR ¹ group; and
A ^- is like an anion.

In the general formula (I), B ^{z + is} preferably

• a) an aromatic, heterocyclic quaternary ammonium compound, for example a quaternary compound of N-methylimidazole,  N-allylimidazole, 2-ethylimidazole or 1,2-dimethyl-imidazole, with these compounds have the positive charge delocalized, or a quaternary compound of pyridine, 4-dimethylaminopyridine, pyrimidine, Pyrazole, N-methyl-pyrazole or quinoline;
• b) a non-aromatic heterocyclic quaternary ammonium connection, for example a quaternary connection of the Diazabicyclo [2,2,2] octane, N-methylmorpholine, N-ethylmorpholine, 1-methylpiperidine or urotropin;
• c) a quaternary alkylammonium compound or arylammonium compound of the formula NR ² R ³ R ⁴ , where R ² , R ³ and R ^{4 can be} identical or different and independently of one another a benzyl radical or phenyl radical, a C ₁ to C ₆ alkyl radical, in particular one C ₁ to C ₄ alkyl radical, for example a methyl radical, an ethyl radical, a propyl radical, an isopropyl radical or a butyl radical, where the abovementioned alkyl radicals can be unsubstituted or substituted by one or more hydroxyl groups or amino groups;
• d) a quaternary phosphonium compound, for example a trialkyl phosphonium compound or triarylphosphonium compound.

B ^{z + is} particularly preferably an N-methylimidazolium compound, a 4-dimethylaminopyridinium compound, a triethylammonium compound, a trimethylammonium compound or a tributylphosphonium group.

In the general formula (I), X preferably represents an oxygen atom or an NR ¹ group, where R ¹ is hydrogen or a methyl radical, an ethyl radical, a propyl radical, an isopropyl radical or a butyl radical, the meaning X being oxygen or a NH group is particularly preferred.

In the general formula (I), Y preferably represents a -CH ₂ group, a -CH ₂ -CH ₂ group, a -CH (CH ₃ ) group, a -CH ₂ -CH ₂ -CH ₂ group or a straight-chain or branched C ₂ -C ₆ -alkylene radical substituted with one or more alkyl groups, hydroxyl groups, amino groups, acyl groups or quaternary ammonium groups, in particular a substituted -CH ₂ -CH ₂ radical or a substituted -CH ₂ -CH ₂ -CH ₂ residue, for example a -CH ₂ -CH (OOCCH ₃ ) -CH ₂ residue; the -CH ₂ group being particularly preferred.

The following compounds in particular can be mentioned as suitable dyes R-XH from the abovementioned classes:
1-chloro-4 - [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yellow No. 12);
1- (2-hydroxyethoxy) -3-methylamino-4-nitrobenzene;
3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow No. 9);
4 - [(2-hydroxyethyl) amino] -3-nitro-1-trifluoromethyl-benzene (HC Yellow No. 13);
4 - [(2-hydroxyethyl) amino] -3-nitro-benzonitrile (HC Yellow No. 14);
4 - [(2-hydroxyethyl) amino] -3-nitro-benzamide (HC Yellow No. 15);
4-amino-2-nitro-diphenylamine (HC Red No. 1);
7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14);
2,4-dinitro-6 - ((2-hydroxyethyl) amino) phenol; 5-chloro-4 - ((2-hydroxyethyl) amino) -2-nitro-aniline; 4 - ((4-dimethylamino) phenyl) azo) aniline;
1- (2-hydroxyethyl) amino-2-nitro-4-diethylamino-benzene;
1- (2-hydroxyethyl) amino-2-nitro-4-dipropylamino-benzene;
N-ethyl-N- (2-hydroxyethyl) -4 - ((4-nitrophenyl) azo) aniline (Cl 11110; Disperse Red No. 1); N- (2-aminoethyl) -4 - ((4-nitrophenyl) azo) aniline;
3-chloro-N, N-di (2-hydroxyethyl) -4 - ((4-nitrophenyl) azo) aniline (Cl 11150; Dis perse Red No. 7);
4 - ((2-chloro-4-nitrophenyl) azo) -N-ethyl-N- (2-hydroxyethyl) aniline (Cl 11115; Disperse Red No. 13);
N, N-Di (2-hydroxyethyl) -3-methyl-4 - ((4-nitrophenyl) azo) aniline (Cl 11210; Disperse Red No. 17);
N, N-Di (2-hydroxyethyl) -4 - ((4-nitrophenyl) azo) aniline (Cl 11130; Disperse Red No. 19);
2 - ((4- (ethyl (2-hydroxyethyl) amino) -2-methylphenyl) azo) -5-nitro-1,3-thiazole (Disperse Blue No. 106);
4 - ((4- (di (2-hydroxyethyl) amino) phenyl) azo) aniline (Disperse Black No. 9);
4 - ((4-aminophenyl) azo) -3-chloro-N, N-di (2-hydroxyethyl) aniline;
6-hydroxy-1- (2-hydroxyethyl) -4-methyl-2-oxo-5-p-tolylazo-1,2-dihydro pyridine-3-carbonitrile;
2,2 '- [Cyclohexylidenebis [(2-methyl-4,1-phenylene) azo]] - bis- [4-cyclohexylphenol] (Cl 21230; Solvent Yellow No. 29);
1 - ((4-aminophenyl) azo) -2-hydroxynaphthalene;
5-amino-2 - ((2-methyl-6-nitrophenyl) azo) phenol;
3-chloro-N, N-di (2-hydroxyethyl) -4 - ((2,6 dichloro-4-nitrophenyl) azo) aniline (Cl 11152; Disperse Brown No. 1);
1,4-diamino-2-methoxy-9,10-anthraquinone (Cl 62015; Disperse Red No. 11);
1-amino-4-hydroxy-9,10-anthraquinone (Cl 60710; Disperse Red No. 15);
1 - ((2-Hydroxyethyl) amino) -4- (methylamino) -9,10-anthraquinone (Cl 61505; Dispense Blue No. 3);
1,4-di ((2-hydroxyethyl) amino) -9,10-anthraquinone (Cl 61545; Dispense Blue No. 23);
1,4-dihydroxy-5,8- (di (2-hydroxyethyl) amino) -9,10-anthraquinone (Cl 62500; Dispense Blue No. 7);
1,4,5,8-tetraamino-9,10-anthraquinone (Cl 64500; Dispense Blue No. 1);
1-amino-4 - ((2-aminoethyl) amino) -2-methyl-9,10-anthraquinone;
1 - ((3-aminopropyl) amino) -9,10-anthraquinone; 1- (3-hydroxypropylamino) anthraquinone; 1 - [(2-Hydroxyethyl) methylamino] anthraquinone;
1,2-dihydroxy-9,10-anthraquinone (alizarin);
2-hydroxy-1,4-naphthalenedione (Cl 75480; Natural Orange 6);
3-Hydroxy-4 - [(4-sulfo-1-naphthalenyl) azo] -2,7-naphthalenedisulfonic acid, trisodium salt (amaranth; Cl 16185; Food Red No. 9);
3,3 ', 4,5,7-pentahydroxyflavone (quercetin);
3,10-diamino-6,13-dichlorotriphendioxazin;
3,10-di ((2-aminoethyl) amino) -6,13-dichlorotriphendioxazine;
3,7-di (4-aminophenyl) -4,8-dichloro-3,7-dihydrobenzo [1,2-b: 4,5-b '] - difuran-2,6-dione;
1,7-Di (4-hydroxy-3-methoxyphenyl) -hepta-1,6-diene-3,5-dione (Natural Yellow No. 7).

In the general formula (I), A is ^- for example a chloride, bromide or iodide anion. However, it is also possible, instead of a halide anion, to use other anions which can be both monovalent and polyvalent, for example a sulfate, phosphate, hydrogen phosphate, carbonate, bicarbonate, oxalate, formate, acetate -, Citrate, tartrate, malonate or pyruvate anion, to be used, the number z of the anions in the case of polyvalent anions having to be divided by the valence of the anion used. The chloride anion is particularly preferred.

The by derivatization of only slightly water-soluble or waterun Soluble dyes obtained new dye derivatives of the formula (I) not only have a significantly improved water solubility, rather these new dye derivatives are also characterized by the same moderate wind-up behavior and great washing stability. The invent dyes according to the invention enable the coloring of keratin fibers, especially of human hair but also of wool or pel zen under gentle and skin-friendly conditions.

Another object of the present invention is therefore an agent for dyeing keratin fibers, especially human hair, which is characterized in that it contains at least one dye derivative of the general formula (I) contains.

The dyes of the formula (I) are in the colorant according to the invention preferably in an amount of 0.01 to 10 percent by weight, in particular containing 0.1 to 8 percent by weight.

For the adjustment of the pH value according to the invention from 2 to 10, before preferably a pH of 3 to 8, especially a neutral to acidic pH from 4 to 7, are both organic and inorganic Suitable acids or bases.  

The following acids are particularly worth mentioning as suitable acids: α-hydroxy carboxylic acids, such as glycolic acid, lactic acid, wine acid, citric acid or malic acid; Ascorbic acid; Gluconic acid lactone; Acetic acid; Hydrochloric acid or phosphoric acid, and mixtures of these Acids.

Suitable bases in particular include the following bases: sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium phosphate, borax (Na ₂ B ₄ O ₇ × 10H ₂ O), disodium hydrogen phosphate, alkanolamines, for example monoethanolamine or triethanolamine, ammonia, aminomethylpropanol and Sodium hydroxide.

If appropriate, the colorant according to the invention can be used in addition to Dye derivatives of the formula (I) also other customary direct compounds Contain dyes on a natural or synthetic basis.

Examples of suitable direct dyes on a natural or synthetic basis are:
1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene;
1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1);
1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue No. 2);
4- [ethyl- (2-hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 12);
4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue No. 11);
1 - [(2,3-Dihydroxypropyl) amino] -4- [methyl- (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue No. 10);
1 - [(2,3-Dihydroxypropyl) amino] -4- [ethyl- (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 9);
1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet No. 2);
1-methylamino-4- [methyl- (2,3-dihydroxypropyl] amino) -2-nitrobenzene (HC Blue No. 6);
2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylamino-benzoic acid (HC Blue No. 13);
1-amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red No. 7);
2-amino-4,6-dinitro-phenol; 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red No. 3);
1-amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red No. 10);
5-chloro-1,4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red No. 11);
1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red No. 13);
4-amino-3-nitrophenol;
4 - [(2-hydroxyethyl) amino] -3-nitrophenol;
1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange No. 2);
4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange No. 3);
4-ethylamino-3-nitrobenzoic acid;
2 - [(4-amino-2-nitrophenyl) amino] benzoic acid;
2-chloro-6-ethylamino-4-nitrophenol;
2-amino-6-chloro-4-nitrophenol;
4 - [(3-hydroxypropyl) amino] -3-nitrophenol;
2,5-diamino-6-nitropyridine;
1,2,3,4-tetrahydro-6-nitroquinoxaline;
4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene;
1 - [(2-Hydroxyethyl) amino] -2-nitrobenzene (HC Yellow No. 2);
1- (2-Hydroxyethoxy) -2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 4);
1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5);
4 - [(2,3-dihydroxypropyl) amino] -3-nitro-1-trifluoromethyl-benzene (HC Yellow No. 6);
2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene;
2-amino-3-nitrophenol;
2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene;
2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow No. 11);
1 - [(2-ureidoethyl) amino] -4-nitrobenzene;
1-chloro-2,4-bis ((2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 10);
2,6-diamino-3 - ((pyridin-3-yl) azo) pyridine;
1,4-di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone;
2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange No. 5);
1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone;
1 - [(3-aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue No. 8);
1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red No. 8);
9- (dimethylamino) benzo [a] phenoxazin-7-ium chloride (Cl 51175; Basic Blue No. 6);
Di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (Cl 42595; Basic Blue No. 7);
3,7-di (dimethylamino) phenothiazin-5-ium chloride (Cl 52015; Basic Blue No. 9);
Di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (Cl 44045; Basic Blue No. 26);
2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methyl sulfate (Cl 11154; Basic Blue No. 41);
8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (Cl 56059; Basic Blue No. 99);
Bis [4- (dimethylamino) phenyl] [4- (methylamino) phenyl] carbenium chloride (Cl 42535; Basic Violet No. 1);
Tris [4- (dimethylamino) phenyl] carbenium chloride (Cl 42555; Basic Violet No. 3);
2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (Cl 45170; Basic Violet No. 10);
Di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (Cl 142510; Basic Violet No. 14);
1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (Cl 21010; Basic Brown No. 4);
1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Cl 12250; Basic Brown No. 16);
1 - [(4-Amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Basic Brown No. 17);
1 - [(4-Amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Cl 12251; Basic Brown No. 17);
3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (Cl 50240;
Basic Red No. 2);
1,4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (Cl 11055; Basic Red No. 22);
2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene chloride (Cl 12245; Basic Red No. 76);
2- [2 - ((2,4-Dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indole-1-ium chloride (Cl 48055; Basic Yellow No. 11);
3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (Cl 12719; Basic Yellow No. 57);
Bis [4- (diethylamino) phenyl] phenylcarbenium hydrogen sulfate (1: 1) (Cl 42040; Basic Green No. 1);
4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow No. 7).

The colorant of the invention can also all for such accessories Horse riding, for example hair dye, known and customary Substitutes, for example perfume oils, complexing agents, waxes, preserves agents, cosmetic resins, such as polyvinylpyrrolidone or Polyvinyl acetate, thickener, alginates, guar gum, hair care substances zen, such as cationic polymers or lanolin derivatives, or Wetting agents and emulsifiers from the classes of anionic, nonioni human, amphoteric or cationic surface-active substances, contain. Wetting agents and emulsifiers are preferably obtained from the Classes of amphoteric or non-ionic surfactant sub punching used. Examples of particularly preferred compounds these classes are betaine surfactants, propionates and glycinates such as Example cocoamphoglycinate or cocoamphodiglycinate, ethoxylated Surfactants with 1 to 1000 ethylene oxide units, preferably with 1 to 300 Ethylene oxide units, such as glyceride alkoxylates, for example as the castor oil, polyglycol ethoxylated with 25 ethylene oxide units amides, ethoxylated alcohols and ethoxylated fatty alcohols (fatty alcohol  alkoxylates) and ethoxylated fatty acid sugar esters, especially ethoxy gated sorbitan fatty acid esters.

The components mentioned are in the usual for such purposes Amounts used, for example the wetting agents and emulsifiers in one Concentration from 0.1 to 30 percent by weight, and the care substances in egg ner amount of 0.1 to 5 weight percent.

In addition to water, the colorant according to the invention can also be organic Solvents such as aliphatic or aromatic alcohols, especially ethanol, isopropanol, 1-methoxypropan-2-ol, 1-ethoxy propan-2-ol, diethylene glycol monomethyl ether or diethylene glycol mono ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, benzyl alcohol, benzyloxyethanol, phenylethyl alcohol, Phenoxyethanol, cinnamon alcohol and glycol ether, in particular 1,2-propanediol, the water content usually being about 25 is up to 95 percent by weight, preferably 30 to 85 percent by weight, while the content of the organic solvent or solution medium mixture is about 5 to 30 percent by weight.

The colorant according to the invention can, especially if it is a Hair dye is in the form of an aqueous or aqueous-alcoholic Lö solution, a cream, a gel, an emulsion or an aerosol present foam, the hair dye both in the form of a One-component preparation as well as in the form of a multi-component preparations, for example in the form of a two-component preparation, in which the dye derivative of formula (I) separately from the other Be components is packaged and the manufacture of the ready-to-use  Hair dye only by mixing immediately before use of the two components takes place, can be assembled.

In the case of a hair dye, the invention is used contemporary colorant by having a sufficient for hair coloring Amount, depending on the length of the hair, about 30 to 120 grams, of the hair dye on the hair, the hair dye at about 15 to 45 degrees Celsius 1 to 60 minutes, preferably 5 to 30 minutes, the hair Rinse thoroughly with water, if necessary wash with a shampoo and finally dries.

An increased fixation of the dye on the hair (i.e. a Improve the stability of the color) by splitting off the cationic radical can be achieved by hydrolysis or aminolysis. This is done by treating the hair with a basic solution (preferably pH = 8 to 10). After an exposure time of about 1 to 15 minutes, preferably 2 to 10 minutes, the hair is thoroughly with Rinsed out water, washed with a shampoo if necessary and finally dried.

In particular, 0.5 to 10 percent are preferred as basic solutions as 1 to 6 percent aqueous solutions of the following compounds Suitable: ammonia, guanidine carbonate, ammonium carbonate or alkali carbonate (for example sodium carbonate), ammonium hydrogen carbonate or alkali hydrogen carbonate (for example sodium hydrogen carbonate) and primary aliphatic amines such as ethanolamine.  

The hair dye according to the invention enables excellent even, intense and extremely permanent coloring of the hair without notable staining of the scalp, ten or more washes survives without noticeable fading of the hair color.

The dye derivatives of the formula (I) according to the invention are simple Way by introducing a cationic group in dyes that have at least one OH or NH group, can be synthesized.

The present invention also relates to a process for the preparation of the dye derivatives of the formula (I), in which in dyes of the formula R-XH (where X is oxygen or an NR ¹ group, where R ¹ is hydrogen or a C ₁ - bis C ₆ -alkyl radical) the corresponding hydroxy group or amino group is halogenoacylated and then the dye haloacyl derivative obtained is reacted with a tertiary amine, a tertiary organophosphorus compound ("tertiary phosphine") or a secondary organic sulfide.

The synthesis of the dyes of the formula (I) according to the invention is summarized in Scheme 1 below, where n and z and the radicals R, X, Y, A ^- , B ^{z +} , which have the meanings given above, A for an anion A ^- corresponding uncharged group and B represents a corresponding tertiary amine or phosphine or a secondary organic sulfide, and Hal corresponds to a halogen atom, preferably a chlorine atom or bromine atom.

Scheme 1

The dye derivatives of the formula (I) are prepared starting from commercially available or easily presentable dyes of the formula R-XH (where X is oxygen or an NR ¹ group, where R ¹ is hydrogen or a C ₁ -C ₆ -alkyl radical) by reaction of the dye with the corresponding halocarboxylic acid halide or halocarboxylic acid anhydride, the corresponding hydroxyl group or amino group being halogenoacylated. The dye haloacyl derivative obtained is then reacted with a tertiary amine, a tertiary phosphine or a secondary organic sulfide to give the cationic dye derivative of the formula (I). The reaction of the halogenacyl derivative with the tertiary amine or the tertiary phosphine or the secondary organic sulfide is preferably carried out in a dipolar aprotic solvent such as, for example, ethyl acetate, dioxane, tetrahydrofuran, dimethylformamide, dichloromethane, dimethyl acetamide, N-methylpyrrolidone, acetonitrile, sulfolane Dimethyl sulfoxide. The above production process can be carried out either in one stage (that is, without isolation of the dye haloacyl derivative) or in two stages (that is, with isolation of the dye haloacyl derivative).

In some cases it may be beneficial to use the above reaction follow the switch. In this case, a cationi cal group and then introduced this cationized carboxylic acid implemented a dye of the formula R-XH. It is also possible to use a a carboxylic acid containing a cationic group, such as React carnitine or betaine with a dye of the formula R-XH.

The following examples are intended to illustrate the subject matter of the invention explain without restricting it to this.  

Examples Manufacturing examples Examples 1 to 58 step 1 Preparation of the Haloacyl Derivatives (Examples 1 to 21)

7 mmol of dye according to Table 1 are in 30 ml of dioxane with 11 mmol Halocarboxylic acid halide for 6 to 8 hours at one temperature of 60 ° C implemented. The red solution obtained is reduced Pressure (water jet vacuum) concentrated and the residue from methylene recrystallized chloride / hexane.

In Examples 1 and 5 to 21, chloroacetyl chloride is used as Halocarboxylic acid halide used, while in Example 2 as Halocarboxylic acid halide bromoacetyl chloride and in Example 3 as Halocarboxylic acid halide 3-chloropropionyl chloride and in Example 4 as halocarboxylic acid halide 2-chloropropionic acid chloride is used.

The output used in the synthesis described above compounds and the end products of the synthesis are shown below Table 1 summarized.  

Table 1

Level 2 Representation of the dye derivatives of the formula (I) (Examples 22 to 58)

4 mmol haloacyl derivative according to Table 2 are in 20 ml of vinegar dissolved ethyl acetate and with 13 mmol of tertiary amine respectively tertiary phosphine added. The reaction mixture is about 20 hours heated under reflux and then evaporated in vacuo. The The residue is recrystallized from isopropanol.

The starting compounds used and end products of Synthesis are summarized in Table 2 below.  

Table 2

Example 59 Two-step synthesis without isolation of the intermediates

23.9 g (0.1 mol) of O-acetylcarnitine hydrochloride are dissolved in 500 ml of water free dichloromethane and dropwise with stirring 11.9 g (0.15 mol) of thionyl chloride were added. The gradually emerging Acid chloride goes into solution. The solvent as well as unreacted Thionyl chloride is distilled off. The residue obtained can vice versa without further purification with the dye to be derivatized be set. For this, 0.1 mol of the dye to be derivatized fes [4 - ((2-chloro-4-nitrophenyl) azo) -N-ethyl-N- (2-hydroxyethyl) aniline (Disperse Red No. 13)] dissolved in 500 ml of anhydrous dichloromethane and with stirring with a 1.5 times molar per free OH group Excess of the O-acetylcarnitine chloride mixture was added. To stirring the reaction mixture at room temperature for six hours 20 ml of anhydrous methanol are added. The reaction mi  The mixture is then stirred for a further 5 minutes. Then be the volatile constituents are distilled off.

It becomes [2-acetoxy-3- (2 - {[4- (2-chloro-4-vitro-phenylazo) phenyl] ethyl amino} ethoxycarbonyl) propyl] trimethyl ammonium chloride (59) The crude product thus obtained can be used directly without further purification can be used in the hair dye according to the invention.

Examples of colorants Examples 60-103 Hair dye

The hair colorants according to Table 3 are either in the form of Staining solution (a) or staining solution (b) prepared and in a for sufficient amount of hair coloring is applied to the hair. After an exposure time of 20 minutes at 40 ° Celsius rinsed the hair with lukewarm water, using a shampoo washed, rinsed again with water and dried.

The intensity of the color obtained is even after ten hair washes been reduced only slightly.

An additional improvement in the washing stability of the coloring can be achieved in this dyeing process in that the Hair after the end of the exposure time of the hair dye, but before rinsing out the dye with a 5 minutes 2 percent aqueous ammonia solution is treated.  

Staining solution a

2.5 mmol of the dye of the formula (I) according to Table 3
10.0 g ethanol
10.0 g polyethylene glycol (20) stearyl ether (25% aqueous solution)
ad 100 g water, fully desalinated

Staining solution b

2.5 mmol dye derivative of the formula (I) according to Table 3
10.0 g ethanol
5.0 g benzyl alcohol
10.0 g polyethylene glycol (20) stearyl ether (25% aqueous solution)
ad 100 g water, fully desalinated

In both staining solutions, sodium carbo is added nat or lactic acid each set a pH of 5.0 to 6.0.

The dyeing results are shown in Table 3 below quantified.  

Table 3

Example 104 Hair dye

1.25 mmol 1- (2 - {[4- (2-chloro-4-nitro-phenylazo) phenyl] ethyl amino} - ethoxycarbonylmethyl) -3-methyl-3H-imidazol-1-ium chloride ( 22)
1.25 mmol di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (Basic Blue No. 26)
1.25 mmol 4- [ethyl- (2-hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 12)
10.0 g ethanol
10.0 g benzyl alcohol
10.0 g polyethylene glycol (20) stearyl ether (25% aqueous solution)
ad 100 g water, fully desalinated

The pH of the coloring solution is brought to 4.8 with sodium carbonate set.

The hair dye is applied to the hair and after a Exposure time of 20 minutes at 40 ° Celsius with lukewarm Water rinsed out. Then the hair is shampooed washed, rinsed again with water and dried. The hair gets a dark purple color (L = 22.3; a = 8.6; b = -11.6).

The intensity of the coloration obtained is also indicated by a ten Sometimes shampooing only slightly reduced.  

The L * a * b * color measurement values determined in the present examples were with a color measuring device from Minolta, type Chromameter II, determined.

The L value stands for the brightness (i.e. the lower the L value) the greater the color intensity), while the a value is a measure of is the red component (i.e. the larger the a value, the larger the Red component). The b-value is a measure of the blue component of the color, whereby the The proportion of blue is greater, the more negative the b value is.

Provide all percentages stated in the present application unless otherwise stated, weight percentages.

Claims (11)

1. Cationic dye derivative of the general formula (I)
where n and z are one or two and the radicals given in the formula (I) have the following meaning:
B ^{z +} is equal to a quaternary ammonium group, a quaternary phosphonium group or a sulfonium group;
Y is an unsubstituted, straight-chain or branched C ₁ to C ₆ alkylene group or a substituted, straight-chain or branched C ₂ to C ₆ alkylene group;
X is oxygen or an NR ¹ group, with R ¹ being hydrogen or a C ₁ to C ₆ alkyl radical;
R is equal to a dye radical, where a suitable dye R-XH is an azo dye, a nitro dye, an anthraquinone dye,
an anthocyanin, a triphendioxazine, a diphenylbenzofurandione or a diphenylbenzopyrrolidone with at least one OH group or an NHR ¹ group is used; and
A ^- is like an anion. 2. dye derivative according to claim 1, characterized in that B ^{z +} for an aromatic, heterocyclic quaternary ammonium compound; a non-aromatic, heterocyclic quaternary ammonium compound; is a quaternary alkylammonium compound or arylammonium compound or a quaternary phosphonium compound. 3. dye derivative according to claim 1 or 2, characterized in that X represents an oxygen atom or an NR ¹ group, with R ¹ being hydrogen or a methyl radical, an ethyl radical, a propyl radical, an isopropyl radical or a butyl radical. 4. Dye derivative according to one of claims 1 to 3, characterized in that Y is a -CH ₂ group, a -CH ₂ -CH ₂ group, a CH (CH ₃ ) group, a -CH ₂ -CH ₂ -CH ₂ group or a straight-chain or branched C ₂ -C ₆ -alkylene radical which is substituted by one or more alkyl groups, hydroxyl groups, amino groups, acyl groups or quaternary ammonium groups. 5. Dye derivative according to one of claims 1 to 4, characterized in that the anion A ^{- is} selected from the following anions: chloride, bromide, iodide, sulfate, phosphate, hydrogen phosphate, carbonate, hydrogen carbonate, oxalate, formate, acetate, citrate, Tartrate, malonate and pyruvate. 6. Agent for dyeing keratin fibers, characterized in that it at least one dye derivative of the formula (I) according to one of the claims Contains 1 to 5. 7. Composition according to claim 6, characterized in that there is one Has a pH of 3 to 8.   8. Composition according to claim 6 or 7, characterized in that it is a Is hair dye. 9. A process for the preparation of the dye derivatives according to any one of claims 1 to 5, in which in dyes of the formula R-XH (where X is oxygen or an NR ¹ group, where R ¹ is hydrogen or a C ₁ - to C ₆ - Alkyl radical) the corresponding hydroxyl group or amino group is halogenoacylated and the dye haloacyl derivative obtained is then reacted with a tertiary amine, a tertiary phosphine or a secondary organic sulfide. 10. The method according to claim 9, characterized in that the Halogen acylation by reacting the dye of the formula R-XH with a halocarboxylic acid halide or halocarboxylic acid anhydride takes place. 11. The method according to claim 9 or 10, characterized in that the implementation of the dye haloacyl derivative with the tertiary Amine, the tertiary phosphine or the secondary organic sulfide in a bipolar aprotic solvent.