WO2002096382A1 - Developer components for oxidation hair dyes - Google Patents

Abstract

The invention relates to p-phenylenediamine derivatives of formula (I), wherein A, B, C and D independently represent -NH2, -NHR or NRaRb- group; R?1 and R2¿ independently represent hydrogen, halogen, a C¿1?-C4-alkyl- or hydroxyalkyl group, a C2-C4-dihydroxyalkyl group or a C?1-C4¿-hydroxyalkoxy group and E represents -O-(C¿n?H2n-y(OH)y)-O-, wherein n is a whole number for 2 to 10 and y is a whole number from 1 to 8, with the proviso that n is bigger than y, or wherein x is a whole number from 1 to 5 and R?3¿ represents hydrogen, halogen, a C¿1?-C4-alkyl or hydroxyalkyl group, a C2-C4-dihydroxyalkyl group or a C1-C4-hydroxyalkoxy group. Said p-phenylenediamine derivatives and their physiologically acceptable salts are suitable as developer components for the production of oxidation dyes for dying particularly human hair.

Description

_ENT W _I CKL _E R _COMPONENTS FOR OXIDATION HAIR COLORS

The invention relates to agents for dyeing keratin fibers which contain new p-phenylenediamine derivatives as developer components, a process for dyeing keratin fibers using these p-phenylenediamine derivatives and new p-phenylenediamine derivatives.

Keratin fibers, especially human hair, are today treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with dyes, tinting agents, waving agents and styling preparations. Means for changing or balancing the color of the scalp hair play an outstanding role.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally sensitive to shampooing, so that a frequently undesired shift in shade or even a visible "discoloration" occurs.

So-called oxidation colorants are used for permanent, intensive dyeings with appropriate fastness properties, which ensure dyeing at relatively low temperatures and in short dyeing times. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or by the action of atmospheric oxygen with one another or by coupling with one or more coupler components. A mixture of a large number of oxidation dye precursors usually has to be used for natural-looking dyeings; in many cases direct dyes are still used for shading.

Good oxidation dye precursors should primarily fulfill the following requirements: they must develop the desired color shades with sufficient intensity and fastness in the oxidative coupling. They must also have a good ability to draw onto the fiber, with no noticeable differences between stressed and freshly regrown hair, especially with human hair (leveling ability). They should be resistant to light, heat, friction and the influence of chemical reducing agents, e.g. Perm liquids. After all, if they are used as hair dye, they should stain the scalp as little as possible, and above all they should be harmless from a toxicological and dermatological point of view. Furthermore, there should be the possibility of easily removing a coloring obtained from the hair by bleaching, if it nevertheless does not correspond to the individual wishes of the individual and should therefore be reversed.

Thanks to constantly changing fads, it is necessary to cover the color palette of hair dyes and tints sufficiently in every color area in order to provide the current trend colors at all times. In many cases this was achieved by varying different dyes, e.g. achieved by the use of 2-nitro-p-phenylenediamine derivatives in the red range, but there is still a constant need for novel oxidation dye precursors which, by means of a suitable combination, enable the above-mentioned parameters to be improved and the largest possible selection of colors.

It has now surprisingly been found that certain bis-p-phenylenediarine derivatives as developer components in oxidizing dyes fulfill this task in an outstanding manner, since they provide intense ruby to dark blue or ruby to dark brown shades with very good lightfastness and excellent washfastness with most of the coupler components. In addition to the excellent fastness properties, the compounds according to the invention are also distinguished due to good solubility in water, good storage stability and outstanding properties from a toxicological point of view and thus represent a significant enrichment of the oxidative hair coloring options.

A first object of the invention is therefore an agent for dyeing keratin fibers, in particular human hair, which contains in a medium suitable for dyeing as oxidation dye precursors at least one developer component which is a p-phenylenediamine derivative of the general formula (I),

in the

A, B, C and D independently of one another represent an -NH ₂ , -NHR or -NR ^a R ^b group in which R, R ^a and R ^b independently of one another represent a dC ₄ -alkyl radical, a C ₂ - C ₄ hydroxyalkyl radical or a C ₂ -C ₄ oligohydroxyalkyl radical,

R ¹ and R ² independently of one another represent hydrogen, halogen, a CrC-alkyl or '-hydroxyalkyl group, a C ₂ -C -dihydroxyalkyl group or a CC ₄ - hydroxyalkoxy group,

- E stands for:

-O- (C _n H _n- y (OH) y) -O- with: n is an integer from 2-10 and y is an integer from 1-8, with the proviso that n is greater than y .

is an integer from 1-5

for hydrogen, halogen, a - -alkyl- or

Hydroxyalkyl group, a C -C ₄ - Dihydroxyalkyl or a C _\ - _C4 -hydroxyalkoxy.

These compounds can be prepared using organic synthesis methods known from the literature. With regard to the detailed preparation instructions, reference is expressly made to the synthesis examples described in the example section.

Since all of the substances according to the invention are diamino compounds, the corresponding acid addition salts can be prepared from them in a conventional manner. All statements in this document and accordingly the claimed scope of protection therefore relate both to the free p-phenylenediamine derivatives of the formula (I) and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. Preferred salts according to formula (I) according to the invention are the hydrochlorides.

Examples of - -alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C ₂ -C ₄ hydroxyalkyl groups are the groups 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-Hydroxyethyl is a particularly preferred hydroxyalkyl group. Inventive examples of C ₂ -C ₄ -Dihydroxyalkylgruppen and Cι-C ₄ - hydroxyalkoxy groups are 2,3-dihydroxybutyl and 2-hydroxy-3-methoxypropyl. According to the invention, preferred halogen substituents are chlorine, bromine and iodine, and chlorine and bromine are particularly preferred.

Compounds of the formula (I) in which the groups A, B, C and D represent -NH ₂ groups are preferred.

Also preferred are compounds of formula (I) in which the radicals R ¹ and R ^{2 are} hydrogen. Furthermore, compounds of the formula (1J are preferred in which n = 2-6, n = 3 and n = 4 are particularly preferred.

A preferred number of hydroxyl groups is y = 1-3, particularly preferred is 1 and 2.

Furthermore, preferred compounds according to the invention are those in which x = 1 and R is hydrogen.

Particularly preferred p-phenylenediamine derivatives of the formula (I) are 1,3-bis- (2 ', 5'-diaminophenoxy) propan-2-ol; 1,4-bis (2 ', 5'-diaminophenoxy) butane-2,3-diol; 2 - ({4- [(2 ', 5'-diaminophenoxy) methyl] phenyl} methoxy) -1, 4-diaminobenzene and 2 - ({2 - [(2', 5'-diaminophenoxy) methyl] phenyl } methoxy) -l, 4-diaminobenzene and their physiologically tolerable salts. The hydrochlorides are particularly preferred physiologically compatible salts of the abovementioned compounds.

As a further component, the agents according to the invention can contain a coupler component. In practice, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are usually used for this.

Coupler components preferred according to the invention are m-aminophenol and its derivatives, such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2, 6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'- Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) benzene, 3-.

Ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1, 3-bis- (2 ', 4'- diaminophenoxy) propane, 1-methoxy-2-amino- 4- (2'-hydroxyethylamino) -benzoI, 1, 3-bis- (2 ', 4'-diaminophenyl) propane, 2,6-bis- (2'- hydroxyethylamino) -1-methylbenzene 1-ethoxy-2-bis- (2'-hydroxyethyl) -amino-4-aminobenzene and l-amino-3-bis- (2'-hydroxyemyl) aminobenzene, o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives, such as, for example, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

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

Quinoxaline derivatives such as 6-methyl-1, 2,3, 4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, l-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-

hydroxyindole,

Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-

Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-

Dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyethyl) - amino-3, 4-methylenedioxybenzene,

Particularly preferred coupler components are resorcinol, 1-naphthol, 2-amino-3-hydroxy-pyridine, 2-methyl-5-amino-phenol, 2,4-diaminophenoxyethanol, 1,3-bis- (2,4-diaminophenoxy ) -propane, 2,6-dimethoxy-3,5-diaminopyridine, 2-chloro-6-methyl-3-aminophenol, 2-methyl-4-chloro-5-aminophenol, l-hydroxy-2-methyl-naphthalene, 6- methoxy-2-methylamino-3-aminopyridine, 2,4-dichloro-3-aminophenol, 1-methoxy-2- amino-4- (2'-hydroxyethyl) aminobenzene, z, / - jumydroxynaphthalene and 2,6-dihydroxy-3, 4-dimethylpyridine.

According to the invention, it can also be preferred to use coupler combinations of two or more coupler components. Couplings of 2-chloro-6-methyl-3-aminophenol / 6-methoxy-2-methylamino-3-aminopyridine, 2-methyl-5-aminophenol / 2,4- are particularly preferred coupler combinations.

Diaminophenoxyethanol, 2,7-dihydroxynaphthalene / 2,6-dimethoxy-3,5-diaminopyridine and 2,6-dihydroxy-3,4-dimethylpyridine / 2,4-dichloro-3-aminophenol.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different coupler components and developer combinations are usually used. Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are usually used as further developer components used.

It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

- G ¹ represents a hydrogen atom, a -CC alkyl radical, a C1-C4 monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a C ₄ ) alkyl radical, a 4'-aminophenyl radical or a d-Gt-alkyl radical who with a β. nitrogen-containing group, a phenyl or a 4'-aminophenyl radical,

- G stands for a hydrogen atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C polyhydroxyalkyl radical, a (C ₁ -C ₄ ) alkoxy (C ₄ -C ₄ ) alkyl radical or a C ₁ -C ₄ alkyl radical which is substituted by a nitrogen-containing group,

- G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ -C ₄ alkyl radical, a QQ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a dQ-hydroxyalkoxy radical a Cι-C ₄ - Acetylaminoalkoxyrest, a C ₁ -C ₄ -Mesylaminoalkoxyrest or Cι-C ₄ - Carbamoylaminoalkoxyrest,

- G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ -C ₄ alkyl radical or

- If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of the C 1 -C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Preferred C 1 -C ₄ alkoxy radicals according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a Cj-Ci-hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. An example of a C ₂ -C ₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, CI atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of formula (II) are especially the amino groups, C ₁ -C ₄ monoalkylamino, Cι-C ₄ dialkylamino, Ct-C ₄ - trialkylammonium groups, C ₁ -C ₄ -Monohydroxyalkylaminogruppen, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p- phenylenediami, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediarnine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (ß-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (ß-hydroxy yl) amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2-fluoro -p-phenylenediamine, 2-isopropyl-p-ρhenylene diamine, N- (ß-hydroxypropyl) -p-phenylene diamine, 2-hydroxymethyl-p-phenylene diamine, N, N-dimethyl-3-methyl-p-phenylene diamine, N, N - (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-Hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-l, 4-dioxane and their physiological tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-toluenediamine, p-phenylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis- (β-hydroxyethyl) -p-phenylenediamine.

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

Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which:

- Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a CrQ-alkyl radical, by a C ₁ -C ₄ -hydroxyalkyl radical and / or by a bridging Y or which is optionally part of a bridging ring system;

- The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or Q-Cs alkoxy groups, or a direct bond,

- G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a C ₁ -C ₄ - Aminoalkyl radical or a direct connection to the bridging Y,

- G, G, G, G, G and G independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C 1 -C ₄ -alkyl radical, with the provisos that the compounds of the formula (E2) only have a bridge Y. contain per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

According to the invention, the substituents used in formula (E2) are defined analogously to the above statements.

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetra-methylenediamine, N, N ' -Bis- (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-bis (ethyl) -N, N'- bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-aminophenyl ) -diaza-cycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) - piperazine, N- (4'-aminophenyl) -p-phenylene clamm and l, 10-bis (2 ', 5'-diaminophenyl) - 1,4,7,10-tetraoxadecane and their physiologically tolerable salts.

Very particularly preferred dinuclear developer components of the formula (E2) are N, N'-bis (β-hydroxy yl) -N, N'-bis- (4'-ammophenyl) -l, 3-diamino-propan-2-ol , Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and l, 10-bis (2 ', 5'-diaminophenyl) -l, 4,7,10-tetraoxadecane or one of its physiologically tolerable salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

in which

G ¹³ represents a hydrogen atom, a halogen atom, a C 1 -C ₄ -alkyl radical, a Ci

C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a (Cj-C ₄ ) -alkoxy-

(-C-C ₄ ) -alkyl radical, a C ₁ -C ₄ -aminoalkyl radical, a hydroxy- (Cι-C ₄ ) -alkylamino radical, a -C-C ₄ -hydroxyalkoxy radical, a C ₁ -C ₄ -hydroxyalkyl- (C ₁ -bis C) -aminoalkyl radical or a (di-Cι-C ₄ alkylamino) - (-C-C) alkyl radical, and

- G ¹⁴ represents a hydrogen or halogen atom, a C ₁ -C ₄ alkyl radical, a CrC ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (Cr C ₄ ) alkoxy- (Cι- C ₄ ) -alkyl radical, a C _ϊ -Q-aminoalkyl radical or a Ci- C ₄ cyanoalkyl radical,

- G ¹⁵ represents hydrogen, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

- G ¹⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are defined analogously to the above statements. Preferred p-aminophenols of the formula (L3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 - amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino- 2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2 - ((Diemylamino) methyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2 - ((diethylamino) methyl) phenol.

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

May further be selected from the developer component ^'from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically acceptable salts. According to the invention, pyrimidine or pyrazole derivatives are preferred.

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5, 6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2.5, 6- triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988, such as 4,5- Diamino-l-methylpyrazole, 4,5-diamino-1 - (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1 - (4'-chlorobenzyl) pyrazole, 4,5-diamino -l, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1 - phenylpyrazole, 4,5-diamino-l-methyl - 5-plιenylpyrazol, 4-amino-l, 3-dimethyl-5-hydrazinopyrazole, 1 -BerLzyl-4,5-diarnino-3-methylpyrazole, 4,5-diamino -3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1 - (β-hydroxyethyl) -3-methylpyrazole, 4.5 -Diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- (4'-methoxyphenyl) -ρyrazole, 4,5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5- Diamino-3-hydroxymethyl-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl-l-isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5- (2'- aminoethyl) amino-l, 3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino- 4 (β-hydroxyethyl) amino-1-methyl-pyrazole.

Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-amino-pyridine, 2 , 3-diamino-6-methoxy-pyridine, 2- (ß-meth-oxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

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

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₄ -C ₄ alkyl radical, an aryl radical, a C ₁ -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical a ( C ₁ -C ₄ ) -Ai'koxy- (C ₁ -C ₄ ) -alkyl radical, a C! -C ₄ -aminoalkyl radical which can optionally be protected by an acetyl-ureide or sulfonyl radical, a (C ₁ -C) alkylamino (C ₁ -C ₄ ) alkyl, a di - [(CrC ₄ ) alkyl] - (C ₁ -C ₄ ) aminoalkyl, the dialkyl optionally having a carbon cycle or a heterocycle 5 or 6 chain links form a C ₁ -C ₄ hydroxyalkyl or a di (C ₁ -C) - [hydroxyalkyl] - (C ₁ -C) aminoalkyl radical, - The X radicals independently of one another represent a hydrogen atom, a dC alkyl radical, an aryl radical, a C ₁ -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a dC ₄ aminoalkyl radical, a (C ₁ -C ₄ ) -Alkylamino- (C ₁ -C) - alkyl radical, a di - [(dC) alkyl] - (C ₁ -C ₄ ) -aminoalkyl radical, the dialkyl radicals optionally having a carbon cycle or a heterocycle with 5 or Form 6 chain links, a dC ₄ -hydroxy alkyl or a di- (-C-C ₄ - hydroxyalkyl) -ammoalkylrest, an amino residue, a dC -alkyl or di- (dC - hydroxyalkyl) -amino residue, a halogen atom, a carboxylic acid group or a sulfonic acid group,

- i has the value 0, 1, 2 or 3,

- p has the value 0 or 1,

- q has the value 0 or 1 and

- n has the value 0 or 1, with the proviso that

- the sum of p + q is not equal to 0,

- if p + q is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

- if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

If the pyrazole- [1,5-a] pyrimidine of the above formula (E4) contains a hydroxyl group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

Among the pyrazole- [1,5-a] -pyrimidines of the above formula (E4) one can mention in particular:

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

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

- pyrazole- (1,5-a] -pyr ιidin-3,5-diamine;

- 2,7-dimethyl pyrazole- [1,5-a] pyrimidm-3,5-diamine;

- 3-amino pyrazol- [1,5-a] pyrimidin-7-ol;

- 3-amino pyrazol- [1,5-a] pyrimidin-5-ol;

- 2- (3-amino pyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;

- 2- (7-amino pyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;

- 2 - [(3-Amino pyrazol- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

- 2 - [(7-Amino pyrazol- [l, 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;

- 5,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

- 2,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

- 2,5, N7, N7-tetramethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine; as well as their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The pyrazole [1,5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

Additional developer components preferred according to the invention are pyrimidine derivatives, pyrazole derivatives, p-aminophenol derivatives and p-diaminobenzene derivatives.

According to the invention, particularly preferred additional developer components are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis- ( ß-Hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2-hydroxy-5-aminophenyl) -methane, N, N'- Bis- (4'- aminophenyl) - 1, 4-diazacycloheptane, 1, 10-bis (2 ', 5'-diaminophenyl) - 1, 4.7, 10-tetra-oxadecane, p-aminophenol, 4-amino -3-methylphenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ((diethylamino) methyl) phenol, 2-amino-4-methylphenol, 2-amino-4-chlorophenol , 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triamino- pyrimidine, 2-hydroxy-4,5,6-triaminopyπmιαιn, 2-dimethylamino-4,5,6-triamino-pyrimidine, 2,4-D ydroxy-5,6-diammopyrimidine, 2,5,6-triaminopyrimidine, l - (2'-Hydroxy-5'-aminobenzyl) imidazolidin-2-one and 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

The hair colorants according to the invention preferably contain both the developer components and the coupler components in an amount of 0.005 to 10% by weight, preferably 0.1 to 5% by weight, based in each case on the total oxidation colorant.

Developer components and coupler components are generally used in approximately molar amounts to one another. If molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can be included.

The agents according to the invention can furthermore contain precursors of nature-analogous dyes. For this purpose, preference is given to using indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. Derivatives of 5,6-dihydroxyindoline of the formula (Ha) are particularly suitable as precursors of nature-analogous hair dyes,

in the independently of each other R ¹ stands for hydrogen, a dC ₄ -allcyi group, a C ₁ -C ₄ hydroxyalkyl group, a C ₃ -C ₆ cycloalkyl group or a C ₂ -C ₄ alkenyl group, in particular a vinyl or allyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation, R ³ stands for hydrogen or a dC ₄ alkyl group,

R ⁴ stands for hydrogen, a C ₁ -C alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C ₄ alkyl group, and R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

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

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially that 5,6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole of the formula (IIb) are also outstandingly suitable as precursors of naturally analogous hair dyes,

in the independently of each other R ¹ stands for hydrogen, a CC -Aiκyιgruppe, a C ₁ -C -hydroxyalkyl group, a C ₃ -C ₆ cycloalkyl group or a C ₂ -C ₄ alkenyl group, in particular one

Vinyl or allyl group

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a dC -alkyl group,

R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which

R represents a dC ₄ alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

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

Within this group, particular mention should be made of N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochlorides, sulfates and hydrobromides, are used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In particular when using dye precursors of the indoline or indole type, it has proven to be advantageous to use an amino acid and / or an oligopeptide as the alkalizing agent. In a preferred embodiment, the hair colorants according to the invention, in addition to the oxidation dye precursors, also remove conventional direct dyes for further modification of the color shades.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2'-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2'-hydroxyethyl) ) -aminophenol, 2- (2 ^, -hydroxyethyl) amino-4,6-dinitrophenol, 1 - (2 ^, -hydroxyethyl) amino-4-methyl-2-nitrobenzene, l-amino-4- (2'-hydroxyethyl) -amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, l- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro l, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-l, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobene zoic acid and 2-chloro-6-ethylamino-l-hydroxy-4-nitrobenzene.

According to the invention, the following can be used as direct dyes:

(a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and

(c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as are mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11.

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

CH ₃ SO ₄ ^"

Cl ^"

The compounds of the formulas (DZl), (DZ3) and (DZ5) are very particularly preferred cationic direct dyes of group (c). 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 dyes that occur naturally, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

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

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

The agents according to the invention can furthermore contain all active substances, additives and auxiliary substances known for such preparations. In many cases, these agents contain at least one surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. 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 z. 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 aniide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and 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 one

Alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16,

Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,

Acyl taurides with 10 to 18 carbon atoms in the acyl group,

Acyl isethionates with 10 to 18 carbon atoms in the acyl group,

Monosulfonic succinate and dialkyl esters with 8 to 18 carbon atoms in the

Alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 C-

Atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 C atoms, linear alpha-olefin sulfonates with 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters 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 carbon atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6

Double bonds according to DE-A-3926 344,

Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22

Represent 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.

Non-ionic surfactants contain z. 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 mol ethylene oxide and / or 0 to 5 mol propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group, C ₁₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula RO- (Z) _χ . These connections are characterized by the following parameters.

The alkyl radical R ^' contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Alkylpolyglycosides in which R consists essentially of C ₈ and C ₁₀ alkyl groups, consists essentially of C ₁₂ - and Cπ-alkyl groups, essentially of C ₈ -C ₁₆ -alkyl groups or essentially of C ₁₂ -Ci ₆ -alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain an average of 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention.

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

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one in the molecule

-COO ^(_) - or -SO ₃ ^H group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimemylammonium glycinate, N-acyl-aminopropyl-N, N-dimethyl-ammonium-glycinate, for example the cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, as well as the cocoacylaniinoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₁₈ 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-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N -alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C 12- 1 ₈ - sarcosine.

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

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

Esterquats are known substances that have both at least one ester function and at least one quaternary ammonium group as a structural element contain. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, a N, N-bis (2-ethyl Palmitoyloxy-) dimemylammom ^'to chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

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

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 Coming 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).

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

The compounds with alkyl groups used as surfactant 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 Mixtures of substances with different alkyl chain lengths depending on the respective raw material.

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. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Furthermore, the agents according to the invention can preferably also contain a conditioning active ingredient selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that have a quaternary nitrogen atom, for example in the form of a

Ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The under the names Merquat ^® 100 (poly (dimethyldiallylammom ^' umchlorid)),

Merquat ^® 550 (pimethyldiallylainmoniumchlorid-acrylamide copolymer) and Merquat ^® 280 (Dimemyldiallyl-anrnioniumchlorid-acrylic acid copolymer commercially available products are examples of such cationic polymers. Copolymers of vinyl pyrrolidone with quaternized derivatives of

Dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such

Compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755

Available commercially.

Vinylpyirolidone-methoimidazolinium chloride copolymers as described under the

Name Luviquat ^® are offered. quaternized polyvinyl alcohol and those under the names

Polyquatium 2,

Polyquaternium 17,

Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the

Polymer backbone. Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow ^Coming® 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).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents. Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimemylaiTunoniumchloride / acrylate-acrylate / acrylate-acrylate / acrylate-acrylate / acrylate-acrylate / acrylate-copolymer / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobomylacrylate 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. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as e.g. polyvinyl alcohol,

Structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,

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,

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active substances which improve the fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,

- Quaternized amines such as methyl 1-alkylamidoemyl-2-akylimidazolinium methosulfate - defoamers like silicones,

Dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

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

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,

Vitamins, provitamins and vitamin precursors, especially those of groups A, B ₃ ,

B ₅ , B ₆ , C, E, F and H,

Plant extracts such as the extracts from green tea, oak bark, nettle,

Witch hazel, hops, chamomile, burdock root, horsetail, white do, linden flowers,

Almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut,

Mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage,

Rosemary, Birch, Mallow, Cuckoo Flower, Quendel, Yarrow, Thyme,

Melissa, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.

Cholesterol,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,

- fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,

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

Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbonates,

Hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary

phosphates,

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

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

pigments

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

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

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, z. B. Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

A second subject of the invention is a process for coloring keratin fibers, in particular hair, using an oxidation colorant according to the invention. The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. The use of hair colorants in a weakly alkaline environment is particularly preferred. The application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. It is also possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for producing oxidizing per compounds and for enhancing the action of a small amount of oxidizing agents present. The enzymes (enzyme class 1: oxidoreductases) can transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase, ascorbate oxidase and laccase are preferred, but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the procedure should be mentioned to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

A third subject of the invention is the use of compounds of the formula (I) as developer components in oxidation colorants for dyeing keratin fibers, in particular hair. New and thus a fourth object of the foundation are the compounds according to formula (I) according to Claim 1, which are characterized by the following combinations of substituents:

The following examples are intended to explain the subject of the invention in more detail.

Examples

1. Synthesis examples

I) Synthesis of I, 3-bis-C2 ', 5'-diaminovhenoxy) -propan-2-ol * 4HCl (El)

a) 1 -Bis- (2'-amino-5'-nitrophenoxy) rjropan-2-ol

A mixture consisting of 23.1 g (0.15 mol) of 2-amino-5-nitrophenol, 27.9 g (0.2 mol) of potassium carbonate and 150 ml of dimethylformamide were heated to approx. 40 ° C. 16.3 g (0.075 mol) l, 3-dibromo-2-propanol were added dropwise and the mixture was then heated to 140 ° C. for 6 hours. After cooling, the reaction mixture was poured onto ice water and the solid which precipitated was filtered off with suction. The crude product was washed with distilled water and dried in vacuo at 70 ° C. The product was olive-colored crystals. Yield: 32 g (58.6% of theory) mp: 222 ° C

b 13-bis- (2'.5'-diaminophenoxy-propan-2-ol * 4HCl

8 g l, 3-bis- (2'-amino-5'-nitrophenoxy) -propan-2-ol were in 100 ml ethanol in the presence of 0.5 g catalyst (5% palladium on carbon) at a pressure of 1 arm. hydrogenated. After the hydrogen uptake had ended, the catalyst was filtered off and the solution was acidified with concentrated HCl. The solvent was then completely removed and the product remained in the form of gray crystals.

II) Synthesis of 1, 4-bis- (2 5-diaminoOhenoxy) butane-2,3-diol * 4HCl (E2)

a) 1,4-bis- (2'-ammo-5'-nittophenoxyVbutan-2,3-diol

The synthesis proceeded analogously to Example Ia), but the starting substances used were 2-amino

5-nitrophenol and 1,4-dibromo-2,3-butanediol. The product could be in the form of yellow

Crystals can be obtained.

M.p .: 243-245 ° C b) 1.4-bis-ι ^/ 2'.5'-diaminor> henoxy ^' ) butane-2.3-diol * 4HCl

The catalytic hydrogenation was carried out analogously to the description of Example Ib), and gray crystals were obtained as the product.

III) Synthesis of 2- (H-ϊ (2 5-diamophenoxy) methyllphenyl} methoxy) -L4-diaminobenzene * 4HCl (E3)

a 2 - ({4-r (2'-amino-5'-nitrophenoxy -m.ethyl] phenyl> memoxyV2-amino-5-nitro-benzene The synthesis proceeded analogously to Example Ia), but the starting substances used were 2-amino- 5-nitrophenol and α, α'-dibromo-p-xylene The product could be obtained in the form of yellow crystals, mp: 120 ° C.

b Synthesis of 2 - ({4-r (2 '_<5'-diaminophenoxy') methyl] phenyl} methoxy -1.4-diaminobenzene * 4HC1

The catalytic hydrogenation was carried out analogously to the description of Example Ib), and gray crystals were obtained as the product.

IV) Synthesis of 2 - ({2 - [(2 5'-diaminophenoxy) methyl] phenyl) methoxy) -l, 4-diaminobenzene * 4HCl (E4)

a) 2 - ({2-r (2'-amino-5'-nitrophenoxy) -methphenylmethoxy-2-amino-5-nitro-benzene The synthesis proceeded analogously to Example Ia), but the starting substances used were 2-amino-5- nitrophenol and α, α'-dibromo-o-xylene. The product could be obtained in the form of yellow crystals.

M.p .: 157 ° C

b) Synthesis of 2-f {2-rf2 \ 5'-diammophenoxy) methyl1phenyl} memoxy) -l, 4-diaminobenzene * 4HC1 The catalytic hydrogenation was carried out analogously to the description of Example Ib), and gray crystals were obtained as the product.

2. Composition of the coloring cream

A base cream of the following composition was produced (unless otherwise stated, all information relates to the mass fraction in g):

Taig fatty alcohol 17.0

Coconut fatty alcohol (C ₁₂ - C ₁₈ ) 4.0

Sodium lauryl ether sulfate (28% solution) 40.0

Cocoamidopropyl betaine (30% solution) 25.0

Cetyl / stearyl alcohol poly (20EO) glycol cup 1.5

Water 12.5

Coloring creams of the following composition were produced:

Base cream 50.0

Developer components 7.5 mmol

Coupler components 7.5 mmol

Na ₂ SO ₃ (inhibitor) 1.0

(NH ₄ ) ₂ SO ₄ 1.0 conc. NH ₃ solution ad pH = 10

Water ad 100 g

In the examples with developer or coupler combination, 3.75 mmol of each of the developers or couplers were used, so that the total amount of developer or coupler was 7.5 mmol / 100 g of the coloring cream.

The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to pH 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water. The oxidative development of the coloring was carried out with 3% hydrogen peroxide solution as the oxidation solution. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.

The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not specially pretreated human hair and left there at 32 ° C for 30 minutes. After the dyeing process was completed, the hair was rinsed, washed with a conventional shampoo and then dried.

The following developer components according to the invention and their combinations with other developers were used for the colorations:

El: 1,3-bis (2 ', 5'-diaminophenoxy) propan-2-ol * 4HCl

(Invention)

E2: 1,4-bis (2 ', 5'-diaminophenoxy) butane-2,3-diol * 4HCl

(Invention)

E3: 2 - ({4 - [(2 ', 5'-diaminophenoxy) methyl] phenyl} -

(According to the invention) methoxy) -1,4-diaminobenzene * 4HC1 E4: 2 - ({2 - [(2 ', 5 ^, -diaminophenoxy) methyl] phenyl} - (according to the invention) methoxy) - 1,4-diaminobenzene * 4HC1

E5 4,5-diamino-l- (2'-hydroxyethyl) pyrazole E6 4- amino-3-methylphenol E7 2-aminomemyl-4-aminophenol E8 2,4,5,6-tetraaminopyrimidine E9 4-hydroxy-2, triaminopyrimidine 5.6

The following compounds were used as coupler components:

Kl resorcinol K2 1 -naphthol K3 2-amino-3-hydroxy-pyridine K4 2-methyl-5-aminophenol

K5 2,4-diaminophenoxyethanol

K6 l, 3-bis (2 ^ 4'-diaminophenoxy) propane

K7 2,6-dimethoxy-3,5-diamino-pyridine

K8 2-chloro-6-methyl-3-aminophenol

K9 2-methyl-4-chloro-5-aminophenol

K10 1-Hydroxy-2-methyl-naphthalene

Kll 6-methoxy-2-methylamino-3-aminopyridine

K12 2,4-dichloro-3-aminophenol

Kl3 1 -ethoxy-2-bis- (2'-hydroxyethyl) amino-4-aminobenzene

K14 1-methoxy-2-amino-4- (2'-hydroxyethyl) aminobenzene

K15 2,7-dihydroxynaphthalene

K16 2,6-dihydroxy-3,4-dimethylpyridine

The following table shows the colorations:

The following dyeing recipes were also produced:

Recipe 1 / color shade: black-blue

Fatty alcohol mixture C ₁₂ -C ₁₈ 6.0%

Eumulgin B2 ¹ 0.4%

TexaponNSO ² 10.0%

Dehyton K ³ 6.5%

Plantacare 1200 ⁴ 1.0%

Mirapol AI 5 ⁵ 2.0%

Sodium metabisulphite 0.2%

Ammonium sulfate 0.5% l, 3-bis (2, '5'-diaminophenoxy) propane-1.13%

2-ol x 4 HCL (El)

N, N-bis (2'-hydroxyethyl) -p-phenylene- 0.29%

Diamine sulfate

1, 3-bis- (N- (2-'hydroxyethyl) -N- (4- 1, 27% aminophenylamino) -2-propanoltetrahydrochloride

Resorcinol 0.055%

4-chlororesorcinol 0.036% m-aminophenol 0.027%

2,4-diaminophenoxyethanol - 0.60% dihydrochloride

2-Amino-4- (2-'hydroxyethylamino) - 0.05% anisole sulfate l, 3-bis (2,4-diaminophenoxy) propane 0.57% tetrahydrochloride

2-amino-3-methylamino-6-methoxy-0.05% pyridine dihydrochloride

5,6-dihydroxyindoline hydrobromide 0.25% Recipe 2 / color shade: dark purple

Fatty alcohol mixture C ₁₂ -C ₁₈ 6.0%

Eumulgin B2 ¹ 0.4%

TexaponNSO ² 10.0%

Dehyton K ³ 6.5%

Plantacare 1200 ⁴ 1.0%

Mirapol A15 ⁵ 2.0%

Sodium metabisulphite 0.2%

Ammonium sulfate 0.5%

1,3-bis- (2,3,5-diaminophenoxy) propane 2.25%

2-ol x 4 HCL (El) p-phenylenediamine 0.05% p-toluenediamine sulfate 0.11%

5-amino-2-methylphenol 0.12%

5- (2 '-hydroxyethylamino) -2-methylphenol 0.08%

3 - amino-2-chloro-6-methylphenol 0.24%

5 - Amino-4-chloro-2-methylρhenol - 0.08% hydrochloride

2,4-dichloro-3-aminophenol hydrochloride 0.10%

1-naphthol 0.07%

1,5-dihydroxynaphthalene 0.16%

2,6-dimethoxy-3,5-diaminopyridine 0.12%

Recipe 3 / color shade: dark brown

Fatty alcohol mixture C ₁₂ -Cιg 6.0%

Eumulgin B2 ¹ 0.4%

Texapon NSO ² 10.0%

Dehyton K ³ 6.5%

Plantacare 1200 ⁴ 1.0%

Mirapol AI 5 ⁵ 2.0%

Sodium metabisulphite 0.2% Ammonium sulfate 0.5%

1, 4-bis (2, '5' -diaminophenoxy) butane 1.2%

2,3-diol x 4 HCL (E2) p-toluenediamine sulfate 0.27% l- (2'-hydroxyethyl) -2,5-diaminobenzene- 0.31% sulfate l, 10-bis- (2 ', 5' -diaminophenyl) -l, 4,7,10- 0,25% tetraoxadecane-tetrahydrochloride p-aminophenol 0.07%

3-methyl-4-aminophenol 0.08%

2-aminomethyl-4-aminophenol 0.13% dihydrochloride

Bis (2-hydroxy-5-aminophenyl) methane 0.19% dihydrochloride o-aminophenol 0.05%

Resorcinol 0.07%

2-methylresorcinol 0.08%

4-chlororesorcinol 0.09% m-aminophenol 0.07%

3 - amino-2-chloro-6-methylphenol 0.39%

3,5-diamino-2-methoxytoluene 0.09%

2,7-dihydroxynaphthalene 0.05%

2-amino-3-hydroxy-pyridine 0.14%

6-hydroxyindole 0.08%

Recipe 4 / color shade: dark magenta

Fatty alcohol mixture d ₂ -C ₁₈ 6.0%

Eumulgin B2 ¹ 0.4%

TexaponNSO ² 10.0%

Dehyton K ³ 6.5%

Plantacare 1200 ⁴ 1.0% 0

Mirapol AI 5 -5 ^D 2.0% Sodium metabisulphite 0.2%

Ammonium sulfate 0.5% 2 - ({4 - [(2 ', 5'-diaminoρhenoxy) methyl] phenyl} - 0.62% memoxy) -l, 4-diaminobenzene x 4 HCL (E3) l- (2'- Hydroxyethyl) -4,5-diamino-0.30% pyrazole sulfate

3-methyl-4-aminophenol 0.1%

2,4,5,6-tettaaminopyrimidine sulfate 0.15%

4-hydroxy-2,5,6-triamino-pyrimidine-0.15% sulfate

5-amino-2-methylphenol 0.05%

5- (2Ηydroxyethylamino) -2-methyl- 0.05% phenol

2,4-dichloro-3-aminophenol hydrochloride 0.27%

2,6-bis (2'-hydroxyethylamino) toluene 0.05% l, 3-bis (2 ', 4 ^c -diaminophenoxy) propane 0.54% tetrahydrochloride

2-amino-3-methylamino-6-methoxy-0.13% pyridine dihydrochloride

2,6-dihydroxy-3,4-dimethylpyridine 0.17%

Recipe 5 / color shade: dark purple

Fatty alcohol mixture Cι ₂ -Cι ₈ 6.0%

Eumulgin B2 ¹ 0.4%

TexaponNSO ² 10.0%

Dehyton K ³ 6.5%

Plantacare 1200 ⁴ 1.0% 0

Mirapol AI 5 ⁵ 2.0%

Sodium metabisulphite 0.2%

Ammonium sulfate 0.5%

2 - ({2- [2, '5'-diaminophenoxy) methyl] phenyl} - 1.24% methoxy) -l, 4-diaminobenzene x 4 HCL (E4) l- (2'-Hydroxyώyl) -2,5-diarxιino- 0.31% benzenesulfate

5-amino-2-methylphenol 0.08%

5 - (2'-Hydroxyethylamino) -2-methyl-0.10% phenol

3 - amino-2-chloro-6-methylphenol 0.10%

2-A_ατino-4- (2'-hydroxyethylamino) - 0.33% anisole sulfate

2-methyl-1-naphthol 0.05%

2-amino-3-methylamino-6- 0.13% methoxypyridine dihydrochloride

The following raw materials are the basis for the coloring recipes:

¹ cetylstearyl alcohol + 20 EO (INCI name: Ceteareth-20) Cognis

² Lauryl ether sulfate sodium salt (approx. 27% active substance) Cognis

³ N, N-djrn ethyl-N- (C _8-18 -kokosamidopropyl) -ammoniumacetobetain (29-32% active substance; INCI name: Aqua, Cocoamidopropyl Betaine) Cognis

⁴ Cπ-i _δ fatty alcohol glucoside (49.5-51.5% active substance; INCI name: Lauryl Glucoside) Cognis

⁵ Poly [N- (3- (dimemylan momum) propyl3-N '- [3-ethyleneoxyethylene-dimethylammonium) propyl] urea di-chloride (INCI name: Polyquaternium-2) Rhodia

Claims

claims

1. Agent for coloring keratin fibers, in particular human hair, containing at least one developer component as dye precursors in a medium suitable for dyeing, characterized in that the developer component is a p-phenylenediamine derivative of the general formula (I),

in the

A, B, C and D independently of one another represent an -NH ₂ , -NHR or -NR ^a R ^b group in which R, R and R independently of one another are a C ₁ -C ₄ -alkyl radical, a C ₂ -C -hydroxyalkyl radical or a C ₂ -C -oligohydroxyalkyl radical,

R ¹ and R ² independently of one another represent hydrogen, halogen, a dC ₄ -alkyl or hydroxyalkyl group, a C ₂ -C -dihydroxyalkyl group or a C ₁ -C ₄ -hydroxyalkoxy group,

- E stands for:

-O- (C _π H _2π - _y (OH) y) -O- with: n is an integer from 2-10 and y is an integer from 1-8, with the proviso that n is greater than y , or

: x is an integer from 1-5

R ³ represents hydrogen, halogen, a dC -alkyl or

Hydroxyalkyl group, a C ₂ -C ₄ -dihydroxyalkyl group or a Ci-C ₄ -hydroxyalkoxy group, or contains its physiologically acceptable salt.

2. Composition according spoke 1, characterized in that the radicals A, B, C and D stand for -NH ₂ groups.

3. Composition according spoke 1 or 2, characterized in that the radicals R ¹ and R ^{2 are} hydrogen.

4. Composition according to claim 1 to 3, characterized in that n = 3 or 4 and y = 1 or 2.

5. Composition according spoke 1 to 3, characterized in that x = 1 and R ^{3 is} hydrogen.

6. Composition according to one of claims 1 to 5, characterized in that the compound of general formula (I) l, 3-bis (2 ', 5'-diaminophenoxy) propan-2-ol, l, 4-bis - (2 ', 5'-diaminophenoxy) butane-2,3-diol, 2 - ({4 - [(2', 5'-diaminophenoxy) methyl] phenyl} meth-oxy) - 1, 4-diaminobeιιzol and 2 - ({2 - [(2 ', 5'-diaminophen-oxy) methyl] phenyl} methoxy) - 1, 4-diaminobenzene or the respective tetrahydrochloride.

7. Composition according to one of claims 1 to 6, characterized in that there is at least one coupler component selected from the group consisting of resorcinol, 1-naphthol, 2-amino-3-hydroxy-pyridine, 2-methyl-5-amino phenol, 2,4-diamino-phenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 2,6-dimethoxy-3,5-diaminopyridine, 2-chloro-6-methyl-3- aminophenol, 2-methyl-4-chloro-5-aminophenol, l-hydroxy-2-methyl-naphthalene, 6-memoxy-2-memylammo-3-aminopyridine, 2,4-dichloro-3-aminophenol, 1-methoxy- Contains 2-amino-4- (2'-hydroxyethyl) aminobenzene, 2,7-dihydroxynaphthalene and 2,6-dihydroxy-3,4-dimethyipyridine.

8. Composition according to one of claims 1-7, characterized in that it contains combinations of two or more coupler components.

9. Composition according spoke 8, characterized in that the coupler combination is selected from 2-chloro-6-methyl-3-aminophenol and 6-memoxy-2-methylamino-3-aminopyridine; 2-methyl-5-aminophenol and 2,4-diaminophenoxyethanol; 2,7-dihydroxy naphthalene and 2,6-dime oxy-3,5-diaminopyridine and 2,6-dihydroxy-3,4-dimethylpyridine and 2,4-dicUor-3-aminophenol.

10. Agent according to one of claims 1 to 9, characterized in that it contains at least one further developer component.

11. Composition according spoke 10, characterized in that the further developer component is selected from p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, N, N-bis (ß-hydroxyethyl) -p -phenylenediamine, N, N'- bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2-hydroxy-5 -aminophenyl) methane, N, N'-bis (4'-aminophenyl) -l, 4-diazacycloheptane, l, 10-bis- (2 ^ 5'-diaminophenyl) -l, 4,7,10-tetra -oxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2- ((diethylamino) methyl) phenol, 2-amino-4 -methylphenol, 2-amino-4-chlorophenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triamino-pyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino -4,5, 6-triamino-pyrimidine, 2,4-dihydroxy-5, 6-diaminopyrimidine, 2,5, 6-triaminopyrimidine, 1 - (2 '-hydroxy-5' -aminobenzyl) - imidazolidin-2-one and 4,5-diamino-l- (2'-hydroxyethyl) pyrazole.

12. Composition according to one of claims 1 to 11, characterized in that it additionally contains a substantive dye.

13. Composition according to one of claims 1 to 12, characterized in that it further contains an anionic, nonionic or cationic polymer.

14. Composition according to one of claims 1 to 13, characterized in that it further contains at least one surfactant.

15. A method for dyeing keratin fibers, in particular human hair, characterized in that an agent according to any one of claims 1 to 14 on the Fasem applied at a temperature between 15 and 40 ° C and rinsed off after an exposure time of 5 to 45 minutes.

16. Use of compounds of formula (I) according to any one of claims 1 to 6 for the oxidative coloring of keratin fibers.

17. Compounds corresponding to formula (I) according to spoke 1, which are characterized by the following combinations of substituents: