DE10260822A1 - New coupler components - Google Patents

Abstract

The present application relates to agents for dyeing keratin fibers, in particular human hair, which contain at least one m-phenylenediamine derivative of the formula (I) in a cosmetically acceptable carrier as a coupler component DOLLAR F1 where DOLLAR AR · 1 ·, R · 2 ·, R · 3 · and R · 4 · independently represent a hydrogen atom, a C¶1¶ to C¶4¶ alkyl group, a C¶2¶ to C¶4¶ monohydroxyalkyl group or a C¶3¶ to C ¶4¶-polyhydroxyalkyl group, DOLLAR AR · 5 · stands for a C¶1¶ to C¶4¶ alkyl group and DOLLAR AX stands for a group of the formula (Ia) DOLLAR A -OC¶n¶H¶2n¶- OC¶m¶H¶2m¶-R · 6 ·, DOLLAR A where DOLLAR AR · 6 · stands for a hydrogen atom, a hydroxy group or a C¶1¶ to C¶4¶ alkoxy group, DOLLAR A n stands for a integer from 2 to 6 and DOLLAR A m represents an integer from 2 to 4, with the proviso that if R · 6 · represents a hydrogen atom, m can also be 1. The coupler components according to the invention enable, in particular in combination with p-toluenediamine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, bis- (2-hydroxy-5- aminophenyl) methane and 4-amino-2-aminomethylphenol, dyeings with high color intensities, good wash resistance and good leveling properties.

Description

The present invention relates to Colorants keratin fibers that contain special m-phenylenediamine derivatives that carry an oxaalkyl ether group, a process for coloring Hair with these agents, as well as some of these m-phenylenediamine derivatives themselves and intermediates, that arise in the production of these connections.

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

As developer components are usually primary aromatic amines with another, in para or ortho position located, free or substituted hydroxyl or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives as well as 2,4,5,6-tetraaminopyrimidine and its derivatives.

Special representatives are, for example p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-aminopyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) diaminopropan-2-ol.

As coupler components are in usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, Pyrazolone and m-aminophenols used. Suitable as coupler substances particularly 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Good oxidation dye precursors should primarily meet the following requirements: the desired oxidative coupling Develop color shades with sufficient intensity and authenticity. she have to also good windability own on the fiber, especially with human hair no noticeable differences between stressed and fresh regrown hair may exist (Leveling). They are said to be constant be against light, warmth, sweat, Friction and the influence of chemical reducing agents, e.g. Perm liquids. Finally should - if as a hair dye coming into use - the Don't stain your scalp too much, and above all, they should be toxicological and dermatological Be harmless. Furthermore, the coloring achieved by bleaching can be easily removed from the hair if it is not the individual wishes corresponds to the individual person and should be undone.

Alone with a developer component or a special coupler / developer combination succeeds in usually not to give a natural shade to the hair receive. In practice, therefore, combinations are usually used various developer and / or coupler components used. It is therefore permanent Need for new, improved dye components that are also in toxicological and dermatological aspects are unproblematic.

Object of the present invention was therefore to develop new coupler components that match the Oxidation dye precursors, in particular in terms of toxicological and dermatological properties, meet and colorations enable in a wide range of colors with good fastness properties.

Surprisingly it has now been found that special m-phenylenediamine derivatives which carry an oxaalkyl ether group, the one placed on coupler components Requirements to a high degree suffice. The coupler components according to the invention enable, especially in combination with p-toluenediamine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, bis (2-hydroxy-5-aminophenyl) methane and 4-amino-2-aminomethylphenol, colorations with high color intensities, good wash resistance and a good leveling ability.

wobei
R¹, R², R³ und R⁴ stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe, eine C₂- bis C₄-Monohydroxyalkylgruppe oder eine C₃- bis C₄-Polyhydroxyalkylgruppe,
R⁵ steht für eine C₁- bis C₄-Alkylgruppe und
X steht für eine Gruppe der Formel (Ia)

wobei
R⁶ steht für ein Wasserstoffatom, eine Hydroxygruppe oder eine C₁- bis C₄-Alkoxygruppe,
n steht für eine ganze Zahl von 2 bis 6 und
m steht für eine ganze Zahl von 2 bis 4, mit der Maßgabe, dass, falls R⁶ für ein Wasserstoffatom steht, m auch 1 sein kann.A first subject of the present invention are therefore agents for coloring keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier as coupler components te at least one m-phenylenediamine derivative of the formula (I)

in which
R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₂ to C ₄ monohydroxyalkyl group or a C ₃ to C ₄ polyhydroxyalkyl group,
R ⁵ represents a C ₁ to C ₄ alkyl group and
X represents a group of the formula (Ia)

in which
R ⁶ represents a hydrogen atom, a hydroxyl group or a C ₁ to C ₄ alkoxy group,
n stands for an integer from 2 to 6 and
m represents an integer from 2 to 4, with the proviso that if R ^{6 represents} a hydrogen atom, m can also be 1.

Among them are keratin fibers furs according to the invention, To understand wool, feathers and especially human hair. Even though the oxidation colorants of the invention primarily for dyeing of keratin fibers are suitable in principle for use also in other areas, especially in color photography, nothing against it.

Since it is in the m-phenylenediamine derivatives according to the invention about amino compounds acts, can be known from these in the usual way Acid addition salts produce. All statements in this document and accordingly the claimed The scope of protection therefore relate both to those in free form Compounds as well as their water-soluble, physiologically compatible Salts. Examples of such Salts are the hydrochlorides, the hydrobromides, the sulfates, the Phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.

Examples of the C ₁ to C ₄ alkyl groups 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 groups. Preferred C ₁ to C ₄ alkoxy groups are the methoxy and ethoxy groups. Further preferred examples of a C ₁ - to C ₄ -monohydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. The other terms used are derived from the definitions given here.

The m-phenylenediamine derivatives of Formula (I) can be made using conventional organic methods produce. An example of this is the test implementation within the scope of the exemplary embodiments directed.

The m-phenylenediamine derivatives of the formula (I) now claimed have not hitherto been described in the literature. However, some structurally related compounds are described in the literature. For example, in the DE-A1-27 37 138 as well as the FR-A-2 486 075 Disclosed m-phenylenediamine derivatives which carry an oxaalkyl ether group in the 1-position. However, these writings do not give any indication of the good coloring properties of the compounds now claimed.

The German writings also disclose DE-A1-26 28 999 such as DE-A1-199 59 318 . DE-A1-199 59 319 and DE-A1-199 59 320 1-alkyl-2-alkoxy-3,5-diaminobenzenes, which differ from the subject matter of the present application by the substituent in the 2-position. The colorations of the compounds now claimed with p-toluenediamine or 1- (2-hydroxyethyl) -2,5-diaminobenzene are in principle similar to those with 2,4-diamino-6-methyl-anisole (prominent representative of the prior art). Surprisingly, the colorations with the m-phenylenediamine derivatives according to the invention are notable for the fact that, in contrast to the colorations with 2,4-diamino-6-methyl-anisole, they are thermally stable and, when heated strongly, as is the case, for. B. occurs when blow drying, do not change.

• – alle Reste R¹, R², R³ und R⁴ für ein Wasserstoffatom stehen oder
• – einer der Reste R¹ und R² sowie einer der Reste R³ und R⁴ für eine 2-Hydroxyethylgruppe stehen und der andere der Reste R¹ und R² sowie der andere der Reste R³ und R⁴ für ein Wasserstoffatom stehen.

According to the invention, the m-phenylenediamine derivatives of the formula (I) in which the radicals R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₁ - to C ₄ monohydroxyalkyl group. Compounds of the formula (I) in which the radicals R ¹ , R ² , R ³ and R ^{4 represent} a hydrogen atom or a 2-hydroxyethyl group are particularly preferred. M-Phenylenediamine derivatives of the formula (I), in which either

• - All radicals R ¹ , R ² , R ³ and R ^{4 represent} a hydrogen atom or
• - One of the radicals R ¹ and R ² and one of the radicals R ³ and R ^{4 represent} a 2-hydroxyethyl group and the others of the radicals R ¹ and R ² and the other of the radicals R ³ and R ^{4 represent} a hydrogen atom.

According to the invention, the m-phenylenediamine derivatives of the formula (I) in which R ^{5 represents} a methyl group can also be preferred.

In a first embodiment, the m-phenylenediamine derivatives of the formula (I) may be preferred in which the unit C _m H _2m R ^{6 represents} a methyl group. In the context of this embodiment, it can be preferred according to the invention if the group C _n H _{2n is} selected from an ethylene group, a propylene group, a butylene group or an i-propylene group. An ethylene group and an i-propylene group are particularly preferred according to the invention.

In a second embodiment, the m-phenylenediamine derivatives of the formula (I) may be preferred in which R ^{6 represents} a C ₁ to C ₄ alkoxy group or a hydroxy group. In the context of this embodiment, it can be preferred according to the invention if the groups C _n H _{2 n} and C _m H _2m are selected independently of one another from an ethylene group, a propylene group, a butylene group or an i-propylene group. An ethylene group and an i-propylene group are particularly preferred according to the invention. In the context of this embodiment, it can be preferred according to the invention if R ^{6 is} selected from an ethoxy group or a methoxy group.

Furthermore, it can be preferred according to the invention if the group X is in the p-position to one of the two amino groups or in the o-position to both amino groups. Furthermore, it can be preferred according to the invention if the group R ^{5 is} in the o or p position to the group X.

According to the invention, the m-phenylenediamine derivatives of formula (I), in which X represents a group which is selected from a 2-methoxyethoxy group, a 2- (2-methoxyethoxy) ethoxy group and one 2- (2-hydroxyethoxy) ethoxy group.

According to the invention, particularly preferred m-phenylenediamine derivatives of formula (I) are selected from the group formed by 3,5-diamino-2- (2-methoxyethoxy) toluene, 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene, 3,5-diamino-4- (2-methoxyethoxy) toluene, 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene and 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene.

Very particularly preferred in the frame In the present invention are 3,5-diamino-2-2-methoxyethoxy) toluene and 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene.

In addition to the m-phenylenediamine derivatives of formula (I) can the colorants of the invention further contain at least one developer component.

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

wobei

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

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

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy radical (C ₁ to C ₄ ) alkyl, a 4'-aminophenyl group or a C ₁ to C ₄ alkyl group which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl group;
• G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C _4- polyhydroxyalkyl, a C ₁ to C ₄ hydroxyalkoxy, a C ₁ to C ₄ acetylaminoalkoxy, a C ₁ to C ₄ mesylaminoalkoxy or a C ₁ to C ₄ carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• - If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-Al form kylendioxo group, such as an ethylenedioxy group.

Examples of the C ₁ to C ₄ alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ to C ₄ hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl 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 the formula (E1) are in particular the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -pphenylendiamin, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane as well as their physiologically compatible Salt.

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

It can continue according to the invention be preferred to use compounds as developer components, that contain at least two aromatic nuclei that are and / or hydroxyl groups are substituted.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄- Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G^{1 2} stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, dass
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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 C ₁ to C ₄ alkyl radical, by a C ₁ to C ₄ hydroxyalkyl radical and / or by a bridging Y. is or is possibly 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 and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl radical or a direct connection to the bridge Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ^{1 2} independently of one another represent a hydrogen atom, a direct bond for bridging Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that
• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

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) tetramethylene diamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylene diamine, Bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically tolerable Salts.

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

Bis- (2-hydroxy-5-aminophenyl) -methane is a whole according to the invention particularly preferred binuclear developer component of the formula (E2).

wobei:

• – G^{1 3} steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁-bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁-bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G^{1 5} steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G^{1 6} steht für Wasserstoff oder ein Halogenatom.

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 ^{1 3} represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C _{1 to} C ₄ ) Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy- (C _{1 to} C ₄ ) -alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, one C ₁ to C ₄ hydroxyalkyl (C _{1 to} C ₄ ) aminoalkyl or a (di-C ₁ to C ₄ alkylamino) (C ₁ to C ₄ ) alkyl, and
• G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,
• G ^{1 5} represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ^{1 6} represents hydrogen or a halogen atom.

The substituents used in formula (E3) are analog according to the invention to the above statements Are defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol as well as their physiologically tolerable Salts.

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

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

Furthermore, the developer component can be selected from heterocyclic developer compo ent, such as the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically acceptable salts.

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

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

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 are described, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3 -dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl -3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- ( 4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4, 5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

• – G¹⁷, G¹⁸, G^{1 9} und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂-bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁-bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁-bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁-bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G^{1 8} und NG^{1 9}G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG^{1 9}G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G ¹⁷ , G ¹⁸ , G ^{1 9} and G ²⁰ independently represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ -bis C ₄ -polyhydroxyalkyl radical is a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical which is optionally substituted by an acetyl-ureide or a sulfonyl radical can be protected, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C _{1 to} C ₄ hydroxyalkyl or a di (C ₁ to C ₄ ) - [hydroxyalkyl] - ( C ₁ - to C ₄ ) -aminoalkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C _{1 to} C ₄ alkyl radical, an aryl radical, a C ₁ to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C _{1 to} C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ to C ₄ hydroxyalkyl or a di (C ₁ to C ₄ hydroxyalkyl) aminoalkyl radical , an amino radical, a C ₁ to C ₄ alkyl or di (C ₁ to C ₄ hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• - the sum of p + q is not equal to 0,
• - If p + q is 2, n has the value 0, and the groups NG ¹⁷ G ^{1 8} and NG ^{1 9} 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 ^{1 9} G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

When the pyrazole [1,5-a] pyrimidine of the above formula (E4) has a hydroxy group on one of the Contains positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is shown for example in the following scheme:

• – Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin; sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.

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-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethylpyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 3-aminopyrazole- [1,5-a] pyrimidin-7-ol;
• - 3-aminopyrazole- [1,5-a] pyrimidin-5-ol;
• - 2- (3-aminopyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;
• - 5,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 3-amino-7-dimethylamino-2,5-dimethylpyrazole [1,5-a] pyrimidine; as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

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

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

As coupler components are in usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, Pyrazolone and m-aminophenol derivatives used. As coupler substances 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene are particularly suitable, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

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

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 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene , 1,3-bis (2 ', 4'-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-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 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Coupler components which are particularly preferred according to the invention are 1-naphthol, 1,5-, 2,7-and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

• – 3,5-Diamino-2-(2-methoxyethoxy)toluol / p-Toluylendiamin,
• – 3,5-Diamino-2-(2-methoxyethoxy)toluol / 1-(2-Hydroxyethyl)-2,5-diaminobenzol,
• – 3,5-Diamino-2-(2-methoxyethoxy)toluol / 4-Amino-2-[(5-amino-2-hydroxyphenyl)methyl]phenol,
• – 3,5-Diamino-2-(2-methoxyethoxy)toluol / 1-(2-Hydroxyethyl)-4,5-diaminopyrazol,
• – 3,5-Diamino-2-[2-(2-methoxyethoxy)ethoxy]toluol / p-Toluylendiamin,
• – 3,5-Diamino-2-[2-(2-methoxyethoxy)ethoxy]toluol / 1-(2-Hydroxyethyl)-4,5-diaminopyrazol,
• – 3,5-Diamino-2-[2-(2-methoxyethoxy)ethoxy]toluol / 1-(2-Hydroxyethyl)-2,5-diaminobenzol,
• – 3,5-Bis-[(2-hydroxyethyl)amino]-2-(2-methoxyethoxy)-toluol / p-Toluylendiamin,
• – 3,5-Bis-[(2-hydroxyethyl)amino]-2-(2-methoxyethoxy)-toluol / 1-(2-Hydroxyethyl)-2,5-diaminobenzol,
• – 3,5-Bis-[(2-hydroxyethyl)amino]-2-(2-methoxyethoxy)-toluol / Bis-(2-hydroxy-5-aminophenyl)methan,
• – 3,5-Bis-[(2-hydroxyethyl)amino]-4-(2-methoxyethoxy)-toluol / p-Toluylendiamin,
• – 3,5-Bis-[(2-hydroxyethyl)amino]-4-(2-methoxyethoxy)-toluol / 1-(2-Hydroxyethyl)-2,5-diaminobenzol sowie
• – 3,5-Bis-[(2-hydroxyethyl)amino]-4-(2-methoxyethoxy)-toluol / Bis-(2-hydroxy-5-aminophenyl)methan.

The following coupler / developer combinations have proven to be particularly suitable according to the invention:

• 3,5-diamino-2- (2-methoxyethoxy) toluene / p-toluenediamine,
• 3,5-diamino-2- (2-methoxyethoxy) toluene / 1- (2-hydroxyethyl) -2,5-diaminobenzene,
• - 3,5-diamino-2- (2-methoxyethoxy) toluene / 4-amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol,
• 3,5-diamino-2- (2-methoxyethoxy) toluene / 1- (2-hydroxyethyl) -4,5-diaminopyrazole,
• 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene / p-toluenediamine,
• - 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene / 1- (2-hydroxyethyl) -4,5-diaminopyrazole,
• 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene / 1- (2-hydroxyethyl) -2,5-diaminobenzene,
• - 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene / p-toluenediamine,
• - 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene / 1- (2-hydroxyethyl) -2,5-diaminobenzene,
• - 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene / bis- (2-hydroxy-5-aminophenyl) methane,
• - 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene / p-toluenediamine,
• - 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene / 1- (2-hydroxyethyl) -2,5-diaminobenzene and
• - 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene / bis (2-hydroxy-5-aminophenyl) methane.

The hair colorants according to the invention contain both the developer components as well as the coupler components are preferred in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, each based on the entire oxidation colorant. Thereby developer components and coupler components generally in approximately molar amounts to one another used. If the molar use also proved to be expedient there is a certain surplus of individuals Oxidation dye precursors 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, may be included.

In another embodiment of the present invention the colorants contain at least one precursor of a natural analog dye. Such indoles are preferred as precursors of nature-analogous dyes and indolines are used 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 hydroxyl group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Derivatives of 5,6-dihydroxyindoline of the formula (IIa) are particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
• - R ² stands for hydrogen or a -COOH group, the -COOH group also as a salt with a physiologically acceptable cation may be present,
• R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ 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 Indolins 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-Dihydroxyindolin-2-carboxylic acid as well as the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.

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

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

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

in the independently of each other

• R ¹ represents hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl 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 C ₁ -C ₄ alkyl group,
• - R ⁴ stands for hydrogen, a C ₁ -C ₄ 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 ,
• - And physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of Indoles 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.

To be highlighted within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5,6-dihydroxyindole.

The indoline and indole derivatives can in the colorants of the invention both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. B. the hydrochloride, of sulfates and hydrobromides. The indole or Indoline derivatives are common in these contained in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In another embodiment it can be preferred according to the invention be the indoline or Indole derivative in colorants in combination with at least one amino acid or an oligopeptide use. The amino acid is advantageously an α-amino acid; all are particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

In addition to the m-phenylenediamine derivatives of the formula (I) according to the invention, in another preferred embodiment of the present invention, the colorants according to the invention can contain one or more direct dyes for shading. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct 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, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis- (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2 - (2'-Hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxy thyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6- Nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro -6-ethylamino-1-hydroxy-4-nitrobenzene.

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

Furthermore, the agents according to the invention can contain a cationic direct dye. Are particularly preferred

• (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) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in US Pat EP-A2-998 908 , to which reference is expressly made at this point, are mentioned in claims 6 to 11.

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

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

The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

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

The preparations according to the invention can also dyes occurring in nature, such as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, Sedre and alkanna root are included.

It is not required that the Oxidation dye precursors or the substantive dyes in each case represent uniform connections. Rather, in the hair colorants according to the invention, conditionally through the manufacturing processes for the individual dyes, additional components may be contained in minor quantities, as far as this is not the coloring result adversely affect or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair colorants and tints according to the invention, reference is further expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for medicines, health products and body care products eV, Mannheim.

The colorants according to the invention can all be used for such Contain preparations known active ingredients, additives and auxiliaries. In many cases contain the colorants at least one surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases However, it has proven to be advantageous to use anionic, select zwitterionic or nonionic surfactants.

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x -CH_Z2-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030 ,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354 ,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344 ,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2–15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts 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 _Z2 -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 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 acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha olefin sulfonates with 12 to 18 carbon 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 C atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030 .
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354 .
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344 .
• - Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

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

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C_{1 2}-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

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 of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C _{1 2} -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 as well
• - Adducts 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 R ¹ O- (Z) _x . These connections are characterized by the following parameters.

The alkyl radical R ¹ 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. Examples of such alkyl radicals are 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.

• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C_{1 2}- und C_{1 4}-Alkylgruppen,
• – im wesentlichen aus C₈- bis C_{1 6}-Alkylgruppen oder
• – im wesentlichen aus C_{1 2}- bis C_{1 6}-Alkylgruppen besteht.

Alkylpolyglycosides in which R ¹

• Essentially from C ₈ and C ₁₀ alkyl groups,
• Essentially from C _{1 2} and C _{1 4} alkyl groups,
• - essentially from C ₈ - to C _{1 6} -alkyl groups or
• - consists essentially of C _{1 2} - to C _{1 6} -alkyl groups.

Any sugar block Z can be used Mono- or oligosaccharides can be used. Usually sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Examples of such sugars are glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, Gulose, Idose, Talose and Sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Is glucose particularly preferred.

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

The alkyl glycosides can besides their surfactant effect also serve to fix fragrance components to improve on the hair. The specialist is therefore in the event that one over the effect of the perfume oil on the duration of the hair treatment the hair desired is preferred to this class of substances as a further ingredient of the preparations according to the invention To fall back on.

Even the alkoxylated homologues of the alkyl polyglycosides mentioned can be used according to the invention become. These homologues can on average up to 10 ethylene oxide and / or propylene oxide units included 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 -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl -3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. 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-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₁ _ _{2 1 8} acyl sarcosine.

According to the invention as cationic surfactants in particular those of the quaternary ammonium compound type, the Esterquats and the Amidoamine used.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as Alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants are preferred 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. 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, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium 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 is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl.

Further usable according to the invention cationic surfactants are the quaternized protein hydrolyzates represents.

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

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".

For the compounds used as surfactants alkyl groups can be uniform substances act. However, it is usually preferred in manufacturing of these substances from native vegetable or animal raw materials to go out, so that you can mix substances with different depend on the respective raw material alkyl chain lengths receives.

In the case of surfactants, the add-on products of ethylene and / or propylene oxide to fatty alcohols or derivatives of these addition products can be both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood as mixtures of homologues that are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. On the other hand, narrow homolog distributions are obtained if, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylaminoethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazoliniummethochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacnlsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstofte wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und N,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstofte wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien, enthalten

Furthermore, the colorants according to the invention can contain further active ingredients, auxiliaries and additives, such as, for example

• Non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - Cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-imidazernolochloro-vinyl-imidazolinolochloro-poly-imidazolinolochloro
• - zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as Polyacnlsäuren, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers,
• Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum 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 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 mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• - Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers like silicones,
• Dyes for coloring the agent,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and N,
• - Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, 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, β-alaninediacetic acid and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• - 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 agents for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - contain antioxidants

Regarding other optional Components as well as the amounts used of these components expressly to the relevant manuals known to those skilled in the art, e.g. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

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

For the purposes of the present invention, aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of a C ₁ -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 actual oxidative coloring of the Fibers can basically done with atmospheric oxygen. However, a chemical one is preferred Oxidizing agents are used, especially if, in addition to the coloring, a lightening effect wanted on human hair is. Persulfates, chlorites and in particular come as oxidizing agents Hydrogen peroxide or its adducts with urea, Melamine and sodium borate in question. According to the invention, however the oxidation colorant can also be applied to the hair together with a catalyst, which the oxidation of the dye precursors, e.g. through atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ^{2 +} , Cu ²⁺ , Fe ^{2 +} , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

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

Suitable enzymes are, for example, peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for this, for example

• Pyranose oxidase and, for example, D-glucose or galactose,
• Glucose oxidase and D-glucose,
• Glycerin oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• - alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or its salts,
• Choline oxidase and choline,
• - Amino acid oxidase and amino acids.

The actual hair dye will be convenient immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the dye precursors, manufactured. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Especially preference is given to using the hair dye in a weakly alkaline Milieu. The application temperatures can range between 15 and 40 ° C lie. After an exposure time of 5 to 45 minutes, it will Hair Dye by rinsing of the one to be colored Hair removed. Washing with a shampoo is not necessary if a high tenside carrier, e.g. a coloring shampoo, was used.

Especially when it is difficult to color Hair can also be prepared with the dye precursors without prior mixing with the oxidation component on the Hair are applied. After an exposure time of 20 to 30 minutes then - if necessary after an intermediate rinse - the oxidation component applied. After a further exposure time of 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to one first variant, in which the preliminary application of the dye precursors a better penetration into the hair is supposed to effect the corresponding Means adjusted to a pH of about 4 to 7. According to one second variant is initially striving for air oxidation, with the applied agent preferred has a pH of 7 to 10. At the subsequent accelerated Postoxidation can be the use of acidified peroxidisulfate solutions as Oxidizing agents may be preferred.

A second subject of the present Registration is the use of the m-phenylenediamine derivatives according to the invention for coloring keratin fibers.

A third subject of the present Invention is a process for dyeing keratin fibers which is a hair dye according to the invention is applied to the fibers and again after a contact time rinsed becomes.

A fourth subject of the present Invention, m-phenylenediamine derivatives are selected from the group that is formed is made of 3,5-diamino-2- (2-methoxyethoxy) toluene, 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene, 3,5-diamino-4- (2-methoxyethoxy) toluene, 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene and 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene.

A fifth subject of the present Invention are the first intermediates in the synthesis of the m-phenylenediamines according to the invention, selected from the group formed by bis (2-chloroethyl) - [2- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate and bis (2-chloroethyl) - [4- (2- methoxyethoxy) -5-methyl-1,3-phenylene] -biscarbamat.

A sixth subject of the present Invention are the second intermediates in the synthesis of the m-phenylenediamines according to the invention, selected from the group formed by 3,3 '- [2- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one) and 3,3' - [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one).

embodiments

1 syntheses

1.1 3,5-diamino-2- (2-methoxyethoxy) toluene

1.1.1 3,5-Dinitro-2- (2-methoxyethoxy) toluene

0.82 g of KOH powder (85%) were suspended in 100 ml of 2-methoxyethanol and heated under reflux until a clear solution was obtained. 10 g of 3,5-dinitro-2-methoxytoluene were then added, and the mixture was heated under reflux for a further 2 h. After cooling, the reaction mixture was poured onto ice water and made alkaline with NaOH. It was extracted several times with methyl tert-butyl ether, and the combined ether phases were cleaned, dried and concentrated on a Rotavapor.

Yield: 8.0 g (66%)

1.1.2 3,5-diamino-2- (2-methoxyethoxy) toluene

6.5 g of 3,5-dinitro-2- (2-methoxyethoxy) toluene, 280 ml of ethanol, 20 ml of water and 0.1 g of Pd / C (5%) were in the autoclave submitted and at 50 ° C. hydrogenated at 50 bar hydrogen pressure for 12 h. Then allowed to cool, the Catalyst was filtered off and the filtrate was on a rotavapor evaporated to dryness. The residue was distilled in a Kugelrohr (0.08 mbar, 185-225 ° C).

Yield: 2.7 g (54%)

1.2 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene

1.2.1 3,5-Dinitro-2- [2- (2-methoxyethoxy) ethoxy] toluene

0.82 g of KOH powder (85%) were suspended in 100 ml of diethylene glycol monomethyl ether, and the approach became reflux heated until a clear solution was obtained. Then 10 g of 3,5-dinitro-2-methoxytoluene was added and the mixture was refluxed for a further 2 h heated. After cooling the reaction mixture was poured onto ice water and made alkaline with NaOH posed. It was extracted several times with methyl tert-butyl ether. The combined ether phases were dried and concentrated on a Rotavapor.

Yield: 9.9 g (70%)

1.2.2 3,5-Diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene

7.7 g of 3,5-dinitro-2- [2- (2-methoxyethoxy) ethoxy] toluene, 280 ml of ethanol, 20 ml of water and 0.1 g of Pd / C (5%) were in the autoclave submitted and at 50 ° C. with 50 bar hydrogen pressure Hydrogenated for 12 h. Afterwards they left cooling down. The catalyst was filtered off and the filtrate was rotavaporated evaporated to dryness. The residue was distilled in a Kugelrohr (0.08 mbar, 220-263 ° C).

Yield: 4.5 g (73%)

1.3 3,5-diamino-4- (2-methoxyethoxy) toluene

1.3.1 3,5-Dinitro-4- (2-methoxyethoxy) toluene

16.4 g of KOH powder (85%) were suspended in 1 l of 2-methoxyethanol, and the mixture is refluxed heated until a clear solution was obtained. Subsequently, 200 g of 2,6-dinitro-4-methylanisole added and heated under reflux for a further 6 h. After cooling the reaction mixture was poured onto ice water and made alkaline with NaOH posed. It was extracted several times with methyl tert-butyl ether. The combined ether phases were dried and concentrated on a Rotavapor.

Yield: 148 g (62%)

1.3.2 3,5-Diamino-4- (2-methoxyethoxy) toluene

145 g of 3,5-dinitro-4- (2-methoxyethoxy) toluene, 1.35 l of ethanol, 150 ml of water and 1 g of Pd / C (5%) were in the autoclave submitted and at 50 ° C. hydrogenated at 50 bar hydrogen pressure for 12 h. Then allowed to cool, the Catalyst was filtered off and the filtrate was on a rotavapor evaporated to dryness. The residue was distilled in the Kugelrohr.

Yield: 102 g (91%)

1.4 3.5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene

1.4.1 3,5-Dinitro-2- (2-methoxyethoxy) toluene

0.82 g of KOH powder (85%) were suspended in 100 ml of diethylene glycol monomethyl ether, and the approach became reflux heated until a clear solution was obtained. Then 10 g of 3,5-dinitro-2-methoxytoluene added and the mixture was heated under reflux for a further 2 h. After cooling the reaction mixture was poured onto ice water and made alkaline with NaOH posed. It was extracted several times with methyl tert-butyl ether. The combined ether phases were dried and concentrated on a Rotavapor.

Yield: 9.9 g (70%)

1.4.2 3,5-Diamino-2- (2-methoxyethoxy) toluene

7.7 g of 3,5-dinitro-2- [2- (2-methoxyethoxy) ethoxy] toluene, 280 ml of ethanol, 20 ml of water and 0.1 g of Pd / C (5%) were in the autoclave submitted and at 50 ° C. with 50 bar hydrogen pressure Hydrogenated for 12 h. Afterwards they left cooling down, the catalyst was filtered off and the filtrate was rotavaporated evaporated to dryness. The residue was distilled in a Kugelrohr (0.08 mbar, 220-263 ° C).

Yield: 4.5 g (73%)

1.4.3 Bis (2-chloroethyl) - [2- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate

38 g of 3,5-diamino-2- (2-methoxyethoxy) toluene and 36 g of calcium carbonate were placed in 1 liter of dioxane and heated to 90 ° C. Within 68 g of 2-chloroethylchloroformate were added over 15 minutes and it was stirred for a further 4 h at this temperature. Then allowed to cool, and the mineral salts were filtered off. The filtrate was poured onto ice water poured, the resulting precipitate was filtered off and in Vacuum dried.

Yield: 65 g (84%)

Melting point: 107 - 109 ° C

1.4.4 3,3 '- [2- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one)

200 ml of sodium hydroxide solution (20%) were submitted and at 45 ° C. heated. This was followed by 65 g of bis (2-chloroethyl) - [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate added in portions. After the addition of 200 ml of dioxane another 2 h at 45 ° C stirred. After stirring overnight at room temperature the mixture was poured onto ice and neutralized with hydrochloric acid. Subsequently was used several times with ethyl acetate extracted. The combined organic phases were in vacuo evaporated to dryness.

Yield: 44 g (87%)

1.4.5 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene

44 g of 3,3 '- [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one) were placed in 500 ml of 20% KOH for 4 hours Reflux heated. After filtration, the mixture was diluted with 200 ml of ethanol and adjusted to pH 8 with HCl. The precipitated salts were filtered off and the filtrate was dried concentrated.

Yield: 37 g (quantitative)

1.5 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxvethoxy) toluene

1.5.1 3,5-Dinitro-4- (2-methoxyethoxy) toluene

16.4 g of KOH powder (85%) were suspended in 1 liter of 2-methoxyethanol, and the mixture was refluxed heated until a clear solution was obtained. Subsequently, 200 g of 3,5-dinitro-4-methoxytoluene was added and the mixture was refluxed for a further 20 h heated. After cooling the reaction mixture was poured onto ice water and made alkaline with NaOH posed. It was extracted several times with methyl tert-butyl ether. The combined ether phases were dried and concentrated on a Rotavapor. Yield: 148 g (62%)

1.5.2 3,5-Diamino-4- (2-methoxyethoxy) toluene

145 g of 3,5-dinitro-2- [2- (2-methoxyethoxy) ethoxy] toluene, 1.35 l of ethanol, 150 ml of water and 1 g of Pd / C (5%) were in the autoclave submitted and at 50 ° C. with 50 bar hydrogen pressure Hydrogenated for 12 h. Afterwards they left cooling down, the catalyst was filtered off and the filtrate was rotavaporated evaporated to dryness. The residue was distilled in the Kugelrohr.

Yield: 102 g (91%)

1.5.3 Bis (2-chloroethyl) - [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate

69 g of 3,5-diamino-2- (2-methoxyethoxy) toluene and 67 g of calcium carbonate were placed in 1 liter of dioxane and heated to 90 ° C. Within 68 g of 2-chloroethylchloroformate were added in the course of 15 minutes, and the mixture was stirred at this temperature for a further 4 h. Then allowed to cool, and the mineral salts were filtered off. The filtrate was poured onto ice water cast. The resulting precipitate was filtered off and in Vacuum dried.

Yield: 116 g (81%)

Melting point: 107-109 ° C

1.5.4 3,3 '- [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one)

400 ml of sodium hydroxide solution (20%) were submitted and at 45 ° C. heated. Subsequently 116 g of bis (2-chloroethyl) - [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate added in portions. After adding 400 ml of dioxane another 2 h at 45 ° C stirred. After stirring overnight at room temperature the mixture was poured onto ice and neutralized with hydrochloric acid. Subsequently was used several times with ethyl acetate extracted and the combined organic phases were in vacuo evaporated to dryness.

Yield: 57 g (61%)

1.5.5 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene

57 g of 3,3 '- [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one) were placed in 500 ml of 20% KOH for 4 hours Reflux heated. After filtration, the mixture was diluted with 200 ml of ethanol and adjusted to pH 8 with HCl. The precipitated salts were filtered off and the filtrate was dried concentrated.

Yield: 44 g (91%)

2 colors

2.1 Carrying out the experiment

For the production of the coloring cream, 50 g of a cream base were weighed into a 250 ml beaker and melted at 80 ° C. The cream base used had the following composition: Hydrenol ^® D 17.0% by weight Lorol ^® tech. 4.0% by weight Texapon ^® NSO 40.0% by weight Dehyton ^® K 25.0% by weight Eumulgin ^® B2 1.5% by weight water 12.5% by weight

1/400 mol of the developer or coupler component separately suspended in distilled water or while heating solved. Subsequently ammonia (<1 ml; 25% ammonia solution) added until the pH was between 9 and 10.

The dissolved dye precursors were one after the other in the hot Cream incorporated. Subsequently was made up to 97 g with distilled water and a pH value with ammonia set from 9.5. After filling up the batch was cold stirred with distilled water to 100 g (<30 ° C.), whereby a homogeneous cream was created.

For the coloring, 25 g of coloring cream were mixed with 25 g of the following oxidizing agent preparation. dipicolinic 0.1% by weight sodium pyrophosphate 0.03% by weight Turpinal ^® SL 1.50% by weight Texapon ^® N28 2.00% by weight Acrysol ^® 22 0.60% by weight Hydrogen peroxide, 50% 12.00% by weight Sodium hydroxide solution, 45% 0.80% by weight water ad 100% by weight

A strand of hair (80% gray; 330 mg to 370 mg in weight) was added to each of the mixtures thus obtained. The mixtures and the strands of hair were then each placed on a watch glass and the strands of hair were well embedded in the coloring creams. After 30 minutes (± 1 minute) of exposure at room temperature, the strands of hair were removed and with an aqueous Texapon ^® EVR solution washed until the excess paint was removed. The strands of hair were air-dried and their shade determined and noted under the daylight lamp (color testing device HE240A) (Taschenlexikon der Farben, A. Kornerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag; Zurich, Göttingen).

The ones obtained from the discoloration studies Results are shown in the tables below.

2.2 Colorings with 3,5-diamino-2- (2-methoxvethoxy) toluene

2.3 Colorings with 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene

2.4 Colorings with 3,5-diamino-4- (2-methoxyethoxy) toluene

2.5 Colorings with 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene

2.6 Colorings with 3,5-bis - [(2-hydroxyethyl] amino] -4- (2-methoxyethoxy) toluene

Claims (16)

Agent for coloring keratin fibers, in particular human hair, containing at least one m-phenylenediamine derivative of the formula (I) in a cosmetically acceptable carrier as a coupler component

where R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a C _{1 to} C ₄ alkyl group, a C ₂ to C ₄ monohydroxyalkyl group or a C ₃ to C ₄ polyhydroxyalkyl group, R ⁵ represents a C ₁ to C ₄ alkyl group and X represents a group of the formula (Ia)

where R ⁶ represents a hydrogen atom, a hydroxyl group or a C ₁ - to C ₄ -alkoxy group, n stands for an integer from 2 to 6 and m stands for an integer from 2 to 4, with the proviso that if R ^{6 represents} a hydrogen atom, m can also be 1. Agent according to Claim 1, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which the radicals R ¹ , R ² , R ³ and R ^{4 represent} a hydrogen atom. Agent according to Claim 1, characterized in that it is an m-phenylenediamine derivative of the formula (I) contains in which one of the radicals R ¹ and R ² and one of the radicals R ³ and R ^{4 represent} a 2-hydroxyethyl group and the other of the radicals R ¹ and R ² and the other of the radicals R ³ and R ^{4 represent} a hydrogen atom stand. Agent according to one of claims 1 to 3, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which R ^{5 represents} a methyl group. Agent according to one of claims 1 to 4, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which the unit C _m H _2m R ^{6 represents} a methyl group. Agent according to one of claims 1 to 4, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which R ^{s is} selected from an ethoxy group or a methoxy group. Agent according to one of claims 1 to 4, characterized in that that it is an m-phenylenediamine derivative of formula (I) contains at the X for a group that selected is composed of a 2-methoxyethoxy group, a 2- (2-methoxyethoxy) ethoxy group and one 2- (2-hydroxyethoxy) ethoxy group. Agent according to claim 1, characterized in that the m-phenylenediamine derivative of formula (I) selected is from 3,5-diamino-2- (2-methoxyethoxy) toluene, 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene, 3,5-diamino-4- (2-methoxyethoxy) toluene, 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene and 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene. Agent according to one of claims 1 to 8, characterized in that that it contains at least one developer component. Agent according to one of claims 1 to 9, characterized in that that it contains at least one further coupler component. Agent according to one of claims 1 to 10, characterized in that that it still contains at least one substantive dye. Agent according to claim 11, characterized in that the substantive dye is cationic. Coloring process keratinic fibers, wherein an agent according to any one of claims 1 to 12 is applied to the fibers and again after an exposure time rinsed becomes. m-phenylenediamine derivatives selected from the group formed is made of 3,5-diamino-2- (2-methoxyethoxy) toluene, 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene, 3,5-diamino-4- (2-methoxyethoxy) toluene, 3,5-bis - [(2-hydroxyethyl) amino] - 2- (2-methoxyethoxy) toluene and 3,5-bis - [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluene. Synthesis intermediates selected from the group formed bis (2-chloroethyl) - [2- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate and bis (2-chloroethyl) - [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate. Synthesis intermediates selected from the group that formed is replaced by 3,3 '- [2- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one) and 3,3 '- [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] bis (1,3-oxazolidin-2-one).