EP1585488A1 - Novel phenylenediamine derivative coupling constituents - Google Patents

Abstract

The invention relates to agents for dyeing keratin fibres, especially human hair, said agents containing at least one m-phenylenediamine derivative of formula (I) in a cosmetically acceptable medium, as a coupling constituent. In said formula (I), R<1>, R<2>, R<3> and R<4> independently represent a hydrogen atom, a C1-C4 alkyl group, a C2-C4 monohydroxyalkyl group or a C3-C4 polyhydroxyalkyl group; R<5> represents a C1-C4 alkyl group; and X represents a group of formula (la), wherein R<6> represents a hydrogen atom, a hydroxy group or a C1-C4 alkoxy group; n represents a whole number between 2 and 6; and m represents a whole number between 2 and 4, provided that, if R<6> represents a hydrogen atom, m can also be 1. The inventive coupling constituents enable dyes to have a very high intensity of colour, very good wash fastness and a very good level dyeing capacity, especially when combined with p-tolylenediamine, 1-(2-hydroxyethyl)-2,5-diaminobenzene, 1-(2-hydroxyethyl)-4,5-diaminopyrazole, bis-(2-hydroxy-5-aminophenyl)methane and 4-amino-2-aminomethylphenol.

Description

 NEW PHENYLENE DIAMINE DERIVATIVE COUPLING COMPONENTS

The present invention relates to agents for dyeing keratin fibers which contain special m-phenylenediamine derivatives which carry an oxaalkyl ether group, a process for dyeing hair using these agents, and some of these m-phenylenediamine derivatives themselves and intermediates which are formed in the preparation of these compounds.

For the coloring of keratin fibers, especially human hair, the so-called oxidation coloring agents play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and

Intermediates. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.

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

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5- Diaminophenyl) ethanol, 2- (2,5-diaminophen.oxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol , 2-hydroxy-4,5,6-triarninopyrimidine, 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) -diamino-propan-2-oI.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. Particularly suitable coupler substances are 1-naphthol, 1,5-, 2,7- and 1, 7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-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 fulfill the following prerequisites: they must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. You must also have a good ability to draw on the fiber, especially in the case of human hair, there must be no noticeable differences between damaged and newly grown hair (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids. After all, if they are used as hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloring achieved should be easily removed from the hair again by bleaching, if it does not correspond to the individual wishes of the individual and is to be reversed.

Alone with a developer component or a special one

Couplers / developer combinations usually fail to achieve a natural shade on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye components which are also problematic in toxicological and dermatological terms.

It was therefore an object of the present invention to develop new coupler components which meet the requirements imposed on oxidation dye precursors, in particular with regard to the toxicological and dermatological properties, and which enable dyeings in a wide color spectrum with good fastness properties.

Surprisingly, it has now been found that special m-phenylenediamine derivatives which carry an oxaalkyl ether group meet the requirements imposed on coupler components to a high degree. The invention Coupler components 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, dyeings with high color intensities, good wash resistance and good leveling capacity.

The present invention therefore firstly relates to agents for dyeing 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.

in which

R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, ad-

C -alkyl group, a C ₂ - to C ₄ -monohydroxyalkyl group or a C ₃ - to C -

polyhydroxyalkyl,

R ⁵ stands for ad- to C ₄ -alkyl group and

X stands for a group of the formula (la)

-OC _n H _2n -OC _m H _2m -R ⁶ (la)

in which

R ⁶ represents a hydrogen atom, a hydroxyl group or a C to C alkoxy group, n represents an integer from 2 to 6 and m represents an integer from 2 to 4, with the proviso that if R ^{6 is} a

Is hydrogen, m can also be 1.

Keratinic fibers are to be understood according to the invention to mean furs, wool, feathers and in particular human hair. Although the oxidation colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent their use in other areas, particularly in color photography. Since the m-phenylenediamine derivatives according to the invention are amino compounds, the known acid addition salts can be prepared from them in the usual way. All statements in this document and accordingly the claimed scope of protection therefore relate both to the compounds present in free form and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.

Examples of the d- 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 d- to C -alkoxy groups are the methoxy and ethoxy groups. Further preferred examples of a C 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 1, 2-dihydroxyethyl. The other terms used are derived from the definitions given here.

The m-phenylenediamine derivatives of the formula (I) can be prepared using conventional organic methods. As an example, reference is made to the experimental procedures in the context of the exemplary embodiments.

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, DE-A1-27 37 138 and FR-A-2 486 075 disclose 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. Furthermore, the German documents DE-A1-26 28 999 and DE-A1-199 59 318, DE-A1-199 59 319 and DE-A1-199 59 320 disclose 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 distinguished by the fact that, in contrast to the colorations with 2,4-diamino-6-methyl-anisole, they are thermally stable and, when heated strongly, as described, for example, in FIG. B. occurs when blow drying, do not change.

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 d- to C ₄ -alkyl group or a d- to C - 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) are very particularly preferred, in which either all the 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 represents} 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.

According to the invention, the m-phenylenediamine derivatives of the formula (!) 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 a / -propylene group. An ethylene group and a / - propylene group are particularly preferred according to the invention.

In the context of a second embodiment, the m-phenylenediamine derivatives of the formula (I) in which R ^{6 is} ad- to C ₄ -alkoxy group or a hydroxyl group can be preferred. In the context of this embodiment, it can be preferred according to the invention if the groups C _n H _2n and C _m H _2m are selected independently of one another from an ethylene group, a propylene group, a butylene group or a / -propylene group. An ethylene group and a / -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 the formula (I) are preferred, in which X represents a group which is selected from a 2-methoxyethoxy group, a 2- (2-methoxyethoxy) ethoxy group and a 2- (2-hydroxyethoxy) ethoxy group.

According to the invention, particularly preferred m-phenylenediamine derivatives of the 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.

3,5-Diamino-2- (2-methoxyethoxy) toluene and 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene are very particularly preferred in the context of the present invention.

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

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

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

in which

G ¹ stands for a hydrogen atom, ad to C ₄ alkyl, ad to C ₄ monohydroxyalkyl, C ₂ to C polyhydroxyalkyl, (d to C) alkoxy (Ci to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C _r to C -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a d to C alkyl radical, a d to C monohydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical or ad- to C -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, ad- to C ₄ -alkyl residue, ad- to C -monohydroxyalkyl residue, a C ₂ - to C ₄ -polyhydroxyalkyl residue, a C to C ₄ hydroxyalkoxy group, a d to C ₄ acetylaminoalkoxy group, a d to C ₄ mesylaminoalkoxy group or a d to C carbamoylaminoalkoxy group;

G ⁴ represents a hydrogen atom, a halogen atom or a d- to C ₄ -alkyl radical or if G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the d- 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. Preferred d- to C-alkoxy radicals according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a d- to C -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 polyhydroxyalkyl group is 1, 2-dihydroxyethyl. 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, d- to C ₄ -monoalkylamino groups, Cr to C ₄ -dialkylamino groups, d- to C ₄ -trialkylammonium groups, d- to C-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- (ß-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-ρ-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N , N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) ~ p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-Ac ethylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically tolerable salts.

P-Phenylenediamine derivatives of the formula (E1) which are very particularly preferred according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.

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

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

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a Cr to C alkyl radical, by a C to C ₄ hydroxyalkyl radical and / or by a bridging Y or which is optionally part of a bridging ring system, the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as, for example, a linear or branched alkylene chain or an alkylene ring, which is formed by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms can be interrupted or terminated and possibly substituted by one or more hydroxyl or C 1 -C ₈ alkoxy radicals, or a direct bond,

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

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridging Y or a d- to C -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.

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

Preferred dinuclear developer components of the formula (E2) are in particular: N, N ^, -Bis (β-hydroxyethyl) -N, N'-bis- (4 ^, -aminophenyl) -1, 3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methyl-aminophenyl) tetramethylene diamine, N, N'-diethyl-N, N ^, bis (4'-amino-3'-methylphenyl) ethylenediamine, 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 acceptable salts.

According to the invention, bis- (2-hydroxy-5-aminophenyl) methane is a very particularly preferred dual-core developer component of the formula (E2).

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

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a d to C alkyl radical, a d to C monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (d to C) alkoxy (C to C ) -alkyl radical, ad- to C ₄ -aminoalkyl residue, a hydroxy- (d- to C ₄ ) -alkylamino residue, ad- to C ₄ -hydroxyalkoxy residue, ad- to C -hydroxyalkyl- (C to C) -aminoalkyl residue or a (di-d to C ₄ alkylamino) - (d to C ₄ ) alkyl radical, and

G ⁴ represents a hydrogen or halogen atom, a C to C ₄ alkyl radical, a Cr to C monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C to C) alkoxy (C to C) alkyl, ad to C ₄ ~ aminoalkyl or C to C cyanoalkyl,

G ¹⁵ represents hydrogen, a C _r to C ₄ alkyl radical, a d to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ^S stands for hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are defined analogously to the above statements. Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (ß-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, ß-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and 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 can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts.

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

Methoxyethyl) ~ amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

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

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4.5 -Diamino-1-methylpyrazole, 4,5- Diamino-1- (ß-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- (ß-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.

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 ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C to C ₄ alkyl radical, an aryl radical, a d to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical (d- to C ₄ ) -alkoxy- (d- to C ₄ ) -alkyl radical, ad- to C -aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (Cr to C ₄ ) -Alkylamino- (C to C ₄ ) -alkyl radical, a di - [(d- to C ₄ ) -alkyl] - (d- to C) -aminoalkyl radical, the dialkyl radicals optionally having a carbon cycle or a heterocycle Form 5 or 6 chain links, a d- to C ₄ -hydroxyalkyl or a di- (d- to C ₄ ) - [hydroxyalkyl] - (d- to C) -aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom , a d- to C alkyl radical, an aryl radical, a d- to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl group, a d- to C ₄ aminoalkyl radical, a (Cr-C) alkylamino - (d- to C) -alkyl radical, a di - [(C to C ₄ ) alkyl] - (d- to C) -aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, a d- to C -hydroxyalkyl radical or a Di- (d- to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, ad- to C -alkyl or di- (C to C - 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 0, if p + q is 2, n is 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3); (5,6); (6,7); (3.5) or (3.7); if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

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

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

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

2,5-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-hydroxy-ethyl) -amino] -ethanol;

2 - [(7-aminopyrazole [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -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 the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

In a further preferred embodiment, the colorants according to the invention contain at least one further coupler component.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Suitable coupler substances are in particular 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-chloro-resorcinol, 4-chloro-resorcinol, 2 -Chlor-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

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 -Dichlor-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4 ^l -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-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy -4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 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.

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 preferably contain both the developer components and the coupler components in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, based in each case on the total oxidation colorant. Developer components and coupler components are generally used in approximately molar amounts to one another. If molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can be included.

In a further embodiment of the present invention, the colorants can contain at least one precursor of a nature-analog dye. Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

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

in the independently of each other

R ¹ represents hydrogen, a dC -alkyl group or a dC -hydroxy-alkyl group,

- R ² represents hydrogen or a -COOH group, the -COOH group also as

Salt with a physiologically compatible cation can be present,

R ³ represents hydrogen or a CC alkyl group,

- R ⁴ stands for hydrogen, a dC ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a dC alkyl group, and

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

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

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

Derivatives of 5,6-dihydroxyindole of the formula (IIb) are also outstandingly suitable as precursors of natural hair dyes, in the independently of each other

R ¹ represents hydrogen, a CC ₄ alkyl group or a dd-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 dC -alkyl group,

- R ⁴ stands for hydrogen, a CC ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a CC 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 indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, 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 are to be emphasized -Dihydroxyindol.

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

In a further embodiment, it can be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular 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-nitroρhenol, 1, 4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2 - (2'-Hydroxyethyl!) Amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5 -chloro-2-nitrobenzene, 4-amino-3-nitrophenol, l- (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 their salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

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 are mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11. Preferred cationic direct dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

he

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly 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 in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

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

With regard to the dyes which can be used in the hair dyeing and toning agents according to the invention, reference is also 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 .: Gh., 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 Personal Care Products, Mannheim.

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

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as z. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, 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 and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps )

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 carbon atoms in the acyl group, acyl isethionates with 10 to 18 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 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. 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 moles of ethylene oxide and / or 0 to 5 moles 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 ₁₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

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

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _χ . 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. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

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

Particularly preferred are alkyl polyglycosides are those in which R ¹ consists essentially of C ₈ - and C ₁₀ alkyl groups, mainly of Cι ₂ - and Cι alkyl groups essentially of C ₈ - to Ci6 alkyl groups or consists essentially of C ₂ - to Ci6 alkyl groups.

Any mono- or oligosaccharides can be used as the sugar building block Z. 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 components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

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

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

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

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are those surface-active compounds that carry at least one quaternary ammonium group and at least one -COO ^Θ - or -Sθ ₃ ^Θ 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 cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate. 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 understood to mean those 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 are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurines, N-alkylsarcosines, 2-alkylamino-propionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C _12-18 acyl sarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the compounds known under the INCl names Quaternium-27 and Quaternium-83 compounds imidazolium. The long alkyl chains of the above-mentioned surfactants preferably have 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, a N, N-bis (2-Palmitoyloxy- ethyl) dimethyl ammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

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

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention. Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow 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, Quatemium-80).

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

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. 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 are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

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, with diethyl sulfate quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone lmidazolinium- methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl trimethyl ammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylates lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate 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 e.g. Polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,

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

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the agent,

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

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

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 needles, horse chestnut, sandalwood, juniper, coconut,

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

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

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

Cholesterol,

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

Fats and waxes such as walrus, beeswax, montan wax and paraffins,

fatty acid,

Complexing agents such as EDTA, NTA, ß-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 agent for hydrogen peroxide and other oxidizing agents,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

- contain antioxidants

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

The agents according to the invention preferably contain the dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the dye precursors into a powdery or tablet-like formulation. For the purposes of the present invention, aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of a dC 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 be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. According to the invention, however, the oxidation coloring agent can also be applied to the hair together with a catalyst which oxidizes the dye precursors, e.g. activated by atmospheric oxygen. 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.

Suitable enzymes are e.g. Peroxidases, which can significantly increase the effects 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 thus 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, e.g.

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 their salts, choline oxidase and choline, amino acid oxidase and amino acids.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. It is particularly preferred to use the hair dye in a weakly alkaline environment. Application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is rinsed off from the hair to be colored. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

In the case of hair that is difficult to dye, the preparation with the dye precursors can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the skin is rinsed and, if necessary, re-shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors is supposed to bring about better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.

A second subject of the present application is the use of the m-phenylenediamine derivatives according to the invention for dyeing keratin fibers. A third object of the present invention is a process for dyeing keratin fibers, in which a hair dye according to the invention is applied to the fibers and rinsed off again after an exposure time.

A fourth object of the present invention are m-phenylenediamine derivatives selected from the group consisting of 3,5-diamino-2- (2-methoxyethoxy) toluene, 3,5-diamino-2- [2- (2-methoxyethoxy) ethoxy] toluene, 3,5-diamino-4- (2-methoxyethoxy) toIuoI, 3,5-bis - [(2-hydroxyethyl) amino] -2- (2-methoxyethoxy) toluene and 3,5-bis- [(2-hydroxyethyl) amino] -4- (2-methoxyethoxy) toluoI.

A fifth object 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] biscarbamate.

A sixth object 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- on).

EXEMPLARY 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 purified, 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 placed in the autoclave and at 50 ° C with 50 hydrogen pressure bar hydrogenated for 12 h. The mixture was then allowed to cool, the catalyst was filtered off and the filtrate was evaporated to dryness on a Rotavapor. The residue was distilled in a Kugelrohr (0.08 mbar, 185-225 ° C). Yield: 2.7 g (54%)

.2 3,5-Diamino-2-r2- (2-methoxyethoχy) ethoxy1toluene

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

0.82 g of KOH powder (85%) was suspended in 100 ml of diethylene glycol monomethyl ether and the mixture was 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-feta-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 placed in the autoclave and at 50 ° C with 50 bar hydrogen pressure hydrogenated for 12 h. Then allowed to cool. The catalyst was filtered off and the filtrate was concentrated to dryness on a Rotavapor. 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 was heated under reflux until a clear solution was obtained. 200 g of 2,6-dinitro-4-methylanisole were then added and the mixture was heated under reflux for a further 6 h. After cooling, the reaction mixture was poured onto ice water and made alkaline with NaOH. It was extracted several times with methyl-fe / τ.-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 3,5-dinitro-4- (2-methoxyethoxy) toluene, 1, 35 l ethanol, 150 ml water and 1 g Pd / C

(5%) were placed in the autoclave and hydrogenated at 50 ° C with 50 bar hydrogen pressure for 12 h. The mixture was then allowed to cool, the catalyst was filtered off and the filtrate was evaporated to dryness on a Rotavapor. The residue was distilled in a Kugelrohr.

Yield: 102 g (91%)

1.4 3,5-bis-r (2-hydroxyethyl) aminol-2- (2-methoxyethoxy) toluene

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

0.82 g of KOH powder (85%) was suspended in 100 ml of diethylene glycol monomethyl ether and the mixture was 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 tetf.-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] toIuol, 280 ml of ethanol, 20 ml of water and 0.1 g of Pd / C (5%) were placed in the autoclave and at 50 ° C with 50 bar hydrogen pressure hydrogenated for 12 h. The mixture was then allowed to cool, the catalyst was filtered off and the filtrate was evaporated to dryness on a Rotavapor. 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 11 dioxane and heated to 90 ° C. 68 g of 2-chloroethyl chloroformate were added over the course of 15 minutes and the mixture was stirred at this temperature for a further 4 hours. The mixture was then allowed to cool and the mineral salts were filtered off. The filtrate was poured onto ice water, the resulting precipitate was filtered off and dried in vacuo.

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 introduced and heated to 45 ° C. 65 g of bis (2-chloroethyl) - [4- (2-methoxyethoxy) -5-methyl-1, 3-phenylene] biscarbamate were then added in portions. After the addition of 200 ml of dioxane, the mixture was stirred at 45 ° C. for a further 2 h. After stirring overnight at room temperature, the mixture was poured onto ice and neutralized with hydrochloric acid. The mixture was then extracted several times with ethyl acetate. The combined organic phases were evaporated to dryness in vacuo. 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 evaporated to dryness. Yield: 37 g (quantitative)

1.5 3,5-bis-r (2-hydroxyethyl) amino1-4- (2-methoxyethoxy) toluene

1.5.1 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 was heated under reflux until a clear solution was obtained. 200 g of 3,5-dinitro-4-methoxytoluene were then added, and the mixture was heated under reflux for a further 20 h. After cooling, the reaction mixture was poured onto ice water given and made alkaline with NaOH. It was extracted several times with methyl-fe / τ.-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 I of ethanol, 150 ml of water and 1 g of Pd / C (5%) were placed in the autoclave and at 50 ° C hydrogenated with 50 bar hydrogen pressure for 12 h. The mixture was then allowed to cool, the catalyst was filtered off and the filtrate was evaporated to dryness on a Rotavapor. The residue was distilled in a 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 11 dioxane and heated to 90 ° C. 68 g of 2-chloroethyl chloroformate were added over the course of 15 minutes, and the mixture was stirred at this temperature for a further 4 hours. The mixture was then allowed to cool and the mineral salts were filtered off. The filtrate was poured onto ice water. The resulting precipitate was filtered off and dried in vacuo.

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 introduced and heated to 45 ° C. 116 g of bis (2-chloroethyl) - [4- (2-methoxyethoxy) -5-methyl-1,3-phenylene] biscarbamate were then added in portions. After adding 400 ml of dioxane, the mixture was stirred at 45 ° C. for a further 2 h. After stirring overnight at room temperature, the mixture was poured onto ice and neutralized with hydrochloric acid. The mixture was then extracted several times with ethyl acetate and the combined organic phases were evaporated to dryness in vacuo. 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 evaporated to dryness. Yield: 44 g (91%)

colorations

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

In each case 1/400 mol of the developer or coupler component was suspended separately in distilled water or dissolved under heating. Then ammonia (<1 ml; 25% ammonia solution) was added until the pH was between 9 and 10.

The dissolved dye precursors were worked into the hot cream one after the other. The mixture was then made up to 97 g with distilled water and the pH was adjusted to 9.5 with ammonia. After filling up to 100 g with distilled water, the mixture was stirred cold (<30 ° C.), a homogeneous cream being formed.

For the coloring, 25 g of coloring cream were mixed with 25 g of the following oxidizing agent preparation.

Dipicolinic acid 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 washed with an aqueous Texapon ^® EVR solution until the excess color 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 results obtained in the coloration tests are shown in the tables below.

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

2.3 Colorings with 3,5-diamino-2-r2- (2-methoxyethoxy) ethoxy1toluene

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

.5 colorations with 3,5-bis - [(2-hvdroxvethvl) aminol-2- (2-methoxyethoxv) toluene

Developer component coloring p-toluenediamine sulfate wine red

2,4,5,6-tetraaminopyrimidine sulfate brown orange p-aminophenol gray red

4,5-diamino-1- (2-hydroxyethyl) pyrazole sulfate dark violet

1- (2-hydroxyethyl) -2,5-diaminobenzene sulfate garnet red

4-amino-3-methylphenol red-brown

4-Amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol dihydrochloride brown violet

2.6 Colorings with 3,5-bis-r (2-hvdroxvethvl) aminol-4- (2-methoxvethoxv -toluene

Developer component coloring p-toluenediamine sulfate dark magenta

2,4,5,6-tetraaminopyrimidine sulfate dusky pink p-aminophenol brown violet

4,5-diamino-1- (2-hydroxyethyl) pyrazole sulfate amaran red

1- (2-hydroxyethyl) -2,5-diaminobenzene sulfate dark violet

4-amino-3-methylphenol brown orange

4-Amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol dihydrochloride gray ruby

More colors

3.1 Recipe 1

Continued recipe 1

Recipe 2

Recipe 3

Continued recipe 3

Recipe 4

Continued recipe 4

Recipe 5

Recipe 6

Recipe 7

Recipe 8

3.9 Colorings

Formulations 1 to 9 were mixed with the above-described oxidizing agent preparation (item 2.1) in a ratio of 1: 1, and the resulting application preparation was applied to strands (Keriing, natural white). After a contact time of 30 minutes at 32 ° C, the fibers were rinsed thoroughly with water, dried with a hair dryer and the coloration was assessed. The following results were obtained:

4 List of the commercial products used

The commercial products used in the examples are defined as follows:

Acid Red 33 Cl 17200 Acid Red 52 Cl 45100 Acrysol ^® 22 acrylic polymer (approx. 29.5 - 30.5% solids in water; INCI name: Acrylates / Steareth-20 methacrylate copolymer)

Akypo Soft 45 NV ^S Lauryl alcohol-4.5-EO-Acetic acid-sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 carboxylate) (Chem-Y)

Aminoxyd ^® WS 35 N, N-Dimethyl-N (C _8- ι ₈ -kokosacylamidopropyl) amine-N-oxide (approx. 35% active substance in water; INCI name: Cocamidopropylamine Oxide) (Goldschmidt)

Basic Orange 31 azo dye (CIBA) Basic Red 51 azo dye (CIBA) Basic Yellow 87 methine dye (CIBA) Celquat ^® L 200 quaternized cellulose derivative (INCI name:

Polyquaternium-4) (National Starch)

Cosmedia Guar ^® C 261 guar hydroxypropyltrimethylammonium chloride (at least 93%

solid body; INCI Name: Guar Hydroxypropyltrimonium Chloride) (Cognis CorporationCosmedia)

Dehydol® LS 2 Cι _2-1 fatty alcohol with approx. 2-EO units (INCI name: Laureth-2) (Cognis Pulcra) Dehyton ^® KN, N-Dimethyl-N- (C _8- ι ₈ -kokosamidopropyl) ammonium aceto-betaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

Dow Corning Q2-140f Dimethylcyclosiloxan Dimethylpolysiloxanol Mixture (approx. 13% solids; INCI name: Cyclomethicone, Dimethiconol) (Dow Corning)

Edenor ^® PK 1805 oleic acid (INCI name: Oleic Acid) (Cognis) Eumulgin ^® B 1 cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis Eumulgin ^® B2 cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) Eumulgin ^® HRE 40 hardened castor oil with approx. 40 EO units (INCI name: Peg-40 Hydrogenated Castor Oil) (Cognis) Eutanol ^® G 2-octyldodecyl alcohol (INCI name: Octyldodecanol) (Cognis) Gafquat ^® 755 dimethylaminoethyl methacrylate-vinylpyrrolidone copolymer , quaternized with diethyl sulfate (approx. 19% solids in water; INCI name: Polyquatemium-11) (ISP)

Gafquat ^® HS 100 vinylpyrrolidone, methacrylamidopropyltrimethylammonium chloride copolymer (19-21% active ingredient in water; INCI name: Polyquaternium-28) (ISP)

Gluadin ^® WQ Wheat Protein Hydrolyzate (approx. 31-35% solids; INCI name: Aqua (Water), Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Ethylparaben, Methylparaben) (Cognis)

HC Red 1 4-amino-2-nitrodiphenylamine HC Red B 54 4 - [(2-hydroxyethyl) amino] -3-nitrophenoI (INCI name: 3-nitro-p-hydroxyethylaminophenol)

HC Red BN 4 [(3-hydroxypropyl) amino] -3-nitrophenol HC Yellow 5 N ¹ - (2-hydroxyethyl) -4-nitro-1,2-phenylenediamine Hydrenol ^® D Ci ₆ -ιs fatty alcohol (INCI name : Cetearyl alcohol) (Cognis)

Kokoslorol ^® Cι _2- ι ₈ fatty alcohol (INCI name: Coconut Alcohol) (Cognis)

Lorol ^® tech. Cι ₂ -ι ₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis)

Luviquat ^® FC 370 vinylimidazolium methochloride-vinylpyrrolidone copolymer (30:70) (38-42% solids in water; INCI name: Polyquatemium-16) (BASF) Merquat ^® 280 dimethyldiallylammonium chloride acrylic acid copolymer (approx. 35 active substance in water; INCI name: Polyquaternium-22) (Ondeo-Nalco)

Merquat ^® 550 dimethyldiallylammonium chloride acrylamide copolymer (approx. 8.1-9.1% active substance in water; INCI name: Polyquatemium-7) (Ondeo-Nalco)

Mirapol ^® A 15 poly [N- (3- (dimethylammonium) propyl] -N ^I - [3-ethyleneoxyethylene dimethyl-ammonium) propyl] urea di-chloride (approx. 64% solids in water; INCI name: polyquaternium -2) (Rhodia)

Natrosol ^® 250 HHR hydroxyethyl cellulose (INCI name: hydroxyethyl cellulose) (Hercules)

Plantaren ^® 1200 UP Cι ₂ -Ci6-fatty alcohol-1.4-glucoside unpreserved, boron-free approx. 50-53% active substance) (Cognis Coφoration (Emery))

Polydiol ^® 400 polyethylene glycol (INCI name: PEG-8) (Cognis) Polymer JR ^® 400 quaternized hydroxyethyl cellulose (INCI name: Polyquaternium-10) (Amerchol)

Polymer ^® W 37194 approx. 20% by weight active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen)

Promois ^® WK Keratin Hydrolyzate (INCI name: Aqua (Water), Hydrolyzed Keratin, Methylparaben, Propylparaben) (Seiwa (Interorgana))

Salcare ^® SC 96 approx. 50% active substance content; INCI name: Polyquatemium-37, Propylene Glycol Dicaprylate / Dicaprate, PPG-1 Trideceth-6 (CIBA)

Stenol ^® 1618 Ci ₆ - s-fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis)

Texapon ^® EVR lauryl ether sulfate sodium salt with special additives (approx. 34 to 37% active substance content; INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis) Texapon ^® K 14 S 70 C lauryl myristyl ether sulfate sodium salt (approx. 68% to 73%

Active substance content ^' ; INCI name: Sodium Myreth Sulfate) (Cognis)

Texapon ^® N28 lauryl ether sulfate sodium salt (at least 26.5%

Active substance content; INCI name: Sodium Laureth Sulfate) (Cognis)

Texapon ^® NSO lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis)

Turpinal ^® SL 1-hydroxyethane-1,1-diphosphonic acid (approx. 58 - 61% active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Westvaco Diacid ^® H 240 4-hexyl-5 (6) -carboxy-2-cyclohexene-1-octanoic acid potassium salt

(Approx. 41% active substance in water) (Westvaco Chemicals)

Claims

claims

1. 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

in which

R \ R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a C to C alkyl group, a C ₂ to C monohydroxyalkyl group or a C ₃ to C -

polyhydroxyalkyl,

R ⁵ represents ad- to C -alkyl group and

X stands for a group of the formula (la)

-OC _n H _2n -OC _m H _2m -R ⁶ (la)

in which

R ⁶ represents a hydrogen atom, a hydroxyl group or a C to C -

Alkoxy group, n is an integer from 2 to 6 and m is an integer from 2 to 4, with the proviso that if R ^{6 is} a

Is hydrogen, 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 radicals R ¹ , R ² , R ³ and R ^{4 represent} a hydrogen atom.

Agent according to Claim 1, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which one of the radicals R ¹ and R ² and one of the radicals R ³ and R ⁴ stand for a 2-hydroxyethyl group and the other of the R ¹ and R ² and the other of R ³ and R ⁴ are hydrogen.

4. Composition 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.

5. Composition 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.

6. Composition according to one of claims 1 to 4, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which R ^{6 is} selected from an ethoxy group or a methoxy group.

7. Composition according to one of claims 1 to 4, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which X for a group selected from a 2-methoxyethoxy group, a 2- (2-methoxyethoxy ) ethoxy group and a 2- (2-hydroxyethoxy) ethoxy group.

8. Composition according to claim 1, characterized in that the m-phenylenediamine derivative of the formula (I) is selected from 3,5-diamino-2- (2-methoxyethoxy) toluoI, 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.

9. Composition according to one of claims 1 to 8, characterized in that it contains at least one developer component.

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

11. Agent according to one of claims 1 to 10, characterized in that it further contains at least one substantive dye.

12. Composition according to claim 11, characterized in that the substantive dye is cationic.

13. A process for dyeing keratin fibers, in which an agent according to one of claims 1 to 12 is applied to the fibers and rinsed off again after an exposure time.

14. m-phenylenediamine derivatives 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.

15. Synthesis intermediates selected from the group consisting of 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.

16. Synthesis intermediates selected from the group consisting of 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).