DE102004029797A1 - Agent for dyeing keratinous fibers - Google Patents

Abstract

The invention relates to derivatives of m-aminophenol according to the formula DOLLAR F1 wherein DOLLAR A È R · 1 · and R · 2 · independently represent a hydrogen atom, a linear or branched C¶1¶-C¶6¶ alkenyl group, a cyclic (C¶3¶-C¶8¶) -alkyl group, a C¶2¶-C¶6¶-alkylene group, an optionally substituted aryl group, an aryl (C¶1¶-C¶6¶) -alkyl group, a C¶1¶-C¶6¶ monohydroxyalkyl group, a C¶2¶-C¶6¶ polyhydroxyalkyl group, a C¶1¶-C¶6¶ alkoxy (C¶1¶-C¶6¶) -alkyl group, a group R ·I ·R ·II ·N- (CH¶2¶) ¶m¶-, wherein R ·I · and R ·II · independently represent a hydrogen atom, a C¶1¶-C ¶6¶-alkyl group, a C¶1¶-C¶6¶-hydroxyalkyl group or an aryl (C¶1¶-C¶6¶) -alkyl group, wherein R · I · and R · II · together with the nitrogen atom can form a 5-, 6- or 7-membered ring, and m is an integer from 2 to 6, DOLLAR A È R · 3 · is a linear or branched C¶1¶-C¶ 8¶-alkyl group, a cyclic (C¶3¶-C¶8¶) alkyl group, a C¶2¶-C¶6¶ alkenyl group, an optionally substituted aryl group, an aryl (C¶1¶-C¶ 6¶) -alkyl group, a C¶1¶-C¶6¶ monohydroxyalkyl group, a C¶2¶-C¶6¶-polyhydroxyalkyl group, DOLLAR A is a group R · III · R · IV · N- (CH¶2 ¶) ¶q¶-, DOLLAR A in which R · III · and R · IV · independently of one another represent a hydrogen atom, a C¶1¶-C¶6¶-alkyl group, a C¶1¶-C¶6¶- Hydroxyalkyl group or an aryl (C¶1¶-C¶6¶) alkyl group, wherein R · III · and R · IV · together with the nitrogen atom can form a 5-, 6- or 7-membered ring, and .. ,

Description

The This invention relates to specific derivatives of m-aminophenol, agents for oxidative dyeing of keratinous fibers, in particular human hair, the contains these derivatives, the use of these derivatives for dyeing keratin-containing fibers, and a corresponding method for dyeing keratin-containing fibers, especially human hair.

For dyeing keratin-containing fibers are generally either direct-acting Dyes or oxidation dyes produced by oxidative coupling one or more developer components with each other or with one or more coupler components arise for use. Coupler and developer components are also known as oxidation dye precursors designated.

When Developer components are usually primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

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

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. As coupler substances Particularly suitable are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monoethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 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, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

Regarding other usual ones Dye components becomes explicit to the series "Dermatology", issued by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, ch. 7, pages 248 - 250 (Direct dyes), and Chap. 8, pages 264-267 (oxidation dyes), as well as the "European Inventory of cosmetic raw materials ", 1996, published by the European Commission, available in Diskette form of the Federal Association of German industrial and commercial enterprises for medicines, Health food and personal care products e.V., Mannheim.

With Oxidation dyes can be intense colorations with good fastness properties achieve. Still problematic is a provision of oxidation hair dyes with sufficient fastness properties, especially in with very good light, washing and rubbing fastness.

dye, containing derivatives of a particularly substituted in 2-position 5-amino-phenols and their use for dyeing keratin-containing fibers are known.

In German Patent Application DE-A1-34 21 694 discloses special 2-alkoxy-5-aminophenol derivatives as a coupler component in oxidative dyeing agents Keratin fibers described.

In German Patent Application DE-A1-31 45 811 discloses special 2-alkoxy-5-aminophenol derivatives as a coupler component in oxidative dyeing agents Keratin fibers are described, with the help of which intensive red colorations can be achieved.

however need the obtained with the known couplers dyeings an improvement the fastness properties, in particular the light fastness.

task It is the object of the present invention to provide colorants for keratin-containing fibers, in particular human ones Hair, provide in terms of color depth, the gray cover and the fastness properties, such as rubbing, washing, welding and cold wave fastness, but especially the light fastness, in particular in the red and brown color range, opposite the Oxidationshaarfärbemitteln of the prior art are improved.

Surprisingly has now been found that the Derivatives of m-aminophenol according to formula I in the presence of developing components keratin fibers oxidative to dye and the resulting colors have excellent fastness properties. They give colorings with exquisite Brilliance and color depth and lead to shades of red and brown.

wobei
R¹ und R² stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder verzweigte C₁-C₈-Alkylgruppe, eine zyklische (C₃-C₈)-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine C₁-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-(C₁-C₆)-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-(C₁-C₆)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können, und m steht für eine ganze Zahl von 2 bis 6,
R³ steht für eine lineare oder verzweigte C₁-C₈-Alkylgruppe, eine zyklische (C₃-C₈)-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine C₁-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe,
eine Gruppe R^IIIR^IVN-(CH₂)_q-,
worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-(C₁-C₆)-alkylgruppe, wobei R^III und R^IV gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können, und q steht für eine ganze Zahl von 2 bis 6,
eine Gruppe -[(CH₂)_x-O-(CH₂)_y]_m-CH₃,
worin m 1 oder 2 ist,
x eine ganze Zahl von 2 bis 6 und
y eine ganze Zahl von 0 bis 6 ist,
R⁴ und R⁵ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine lineare oder verzweigte C₁-C₆-Alkylgruppe, eine Nitrogruppe, eine Carboxylgruppe, eine Cyanogruppe, eine Hydroxygruppe, eine C₁-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine Hydroxy-(C₁-C₆)-alkoxygruppe,
eine Gruppe R^VR^VIN-(CH₂)_s-,
worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und s steht für eine ganze Zahl von 0 bis 6,
n steht für eine ganze Zahl von 0 bis 6,
mit der Maßgabe, dass, wenn n gleich Null ist und R³ für ein Wasserstoffatom, eine Methylgruppe oder eine 2-Hydroxyethylgruppe steht, mindestens ein Rest aus R¹, R², R⁴ und R⁵ kein Wasserstoffatom bedeutet.A first subject of the invention are m-aminophenol derivatives according to formula I and its salts,

in which
R ¹ and R ² independently of one another represent a hydrogen atom, a linear or branched C ₁ -C ₈ -alkyl group, a cyclic (C ₃ -C ₈ ) -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an aryl (C ₁ -C ₆ ) alkyl group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy (C ₁ -C ₆ ) alkyl group, a group R ^I R ^II N- (CH _{2) m} - wherein R ^I and R ^II are independently a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, or an aryl ( C ₁ -C ₆ ) -alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring, and m is an integer from 2 to 6,
R ³ is a linear or branched C ₁ -C ₈ alkyl group, a cyclic (C ₃ -C ₈ ) alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an aryl (C ₁ -C ₆ ) -alkyl group, a C ₁ -C ₆ -monohydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group,
a group R ^III R ^IV N- (CH ₂ ) _q -,
wherein R ^III and R ^IV independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or an aryl (C ₁ -C ₆ ) alkyl group, wherein R ^III and R ^IV together with the nitrogen atom can form a 5-, 6- or 7-membered ring, and q stands for an integer from 2 to 6,
a group - [(CH ₂ ) _x -O- (CH ₂ ) _y ] _m -CH ₃ ,
wherein m is 1 or 2,
x is an integer from 2 to 6 and
y is an integer from 0 to 6,
R ⁴ and R ⁵ independently represent a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ alkyl group, a nitro group, a carboxyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ monohydroxyalkyl group, a C C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a hydroxy (C ₁ -C ₆ ) alkoxy group,
a group R ^V R ^VI N- (CH ₂ ) _s -,
wherein R ^V and R ^VI independently represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and s is an integer of 0 until 6,
n is an integer from 0 to 6,
with the proviso that when n is zero and R ^{3 is} a hydrogen atom, a methyl group or a 2-hydroxyethyl group, at least one of R ¹ , R ² , R ⁴ and R ⁵ does not represent a hydrogen atom.

In a preferred embodiment of the invention in formula I n is 0 or 1.

It is inventively preferred that at least one radical R ¹ or R ^{2 of} the formula I for a water substance atom.

In formula I, R ¹ particularly preferably represents a hydrogen atom and R ² particularly preferably represents a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -monohydroxyalkyl group and a C ₂ -C ₆ -polyhydroxyalkyl group.

The radical R ^{3 of} the formula I preferably represents a linear, in particular branched, C ₃ -C ₈ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl, in particular phenyl or a group - [(CH ₂ ) _x -O- (CH ₂ ) _y ] _m -CH ₃ , in which x, y and m are defined as described above.

It is further preferred that when in formula I the radical R ^{3 is} a group - [(CH ₂ ) _x -O- (CH ₂ ) _y ] _m -CH ₃ , x is 2, y is 0 and m is equal to 1 or 2.

The radical R ³ according to formula I particularly preferably represents isopropyl, vinyl, allyl, an optionally substituted phenyl group and a group - [(CH ₂ ) _x -O- (CH ₂ ) _y ] _m -CH ₃ , in which m is 1 , x is 2 and y is 0.

The radicals R ⁴ and R ^{5 of} the formula I are preferably, independently of one another, a hydrogen atom, a chlorine atom, a methyl group or a methoxy group.

Preferably are the compounds according to formula I selected from the group consisting of 5-amino-2- [2- (2-methoxyethoxy) ethoxy] phenol, 5-amino-2- (2-isopropoxyethoxy) phenol, 5-amino-2- (2-phenoxyethoxy) phenol, 2- (2-isopropoxyethoxy) -5- (methylamino) phenol, 5 - [(2-hydroxyethyl) amino] -2- (2-isopropoxy-ethoxy) phenol, 5 - [(2-hydroxyethyl) amino] -2- [2- (2-methoxyethoxy) ethoxy] phenol, 2- [2- (2-methoxyethoxy) ethoxy] -5- (methylamino) phenol, 5- (methylamino) -2- (2-phenoxyethoxy) phenol, 5 - [(2-hydroxyethyl) amino] -2- (2-phenoxyethoxy) phenol and the physiologically acceptable Salts of the aforementioned compounds.

If the compounds of the invention are present as salts, these are preferably by reacting the Compounds according to formula I formed with organic or inorganic acids. The salts are preferably physiologically tolerated.

In the following, examples of the groups or radicals mentioned as substituents in the context of this application will be mentioned. Examples of linear and branched C ₁ -C ₈ -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Examples of cyclic (C ₃ -C ₈ ) -alkyl groups are cyclopentyl and cyclohexyl.

Examples of preferred C ₂ -C ₆ alkenyl radicals are vinyl and allyl.

C ₁ -C ₆ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group.

Further, as preferable examples of a C ₁ -C ₆ monohydroxyalkyl group, there may be mentioned hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl to be named. A 2-hydroxyethyl group is particularly preferred.

Examples of a C ₂ -C ₆ polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and methoxyhexyl groups are examples of C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl groups according to the invention.

A preferred hydroxy C ₁ -C ₆ alkoxy group is the 2-hydroxyethoxy group. Preferred aryl groups are phenyl, naphthyl and biphenyl.

Examples for halogen atoms are F, Cl, Br or I atoms, with Cl and Br atoms being most preferred are.

Preferred aryl-C ₁ -C ₆ -alkyl groups are benzyl and 2-phenylethyl.

The amino, diethylamino, dimethylamino, di (2-hydroxyethyl) amino, (2-hydroxyethyl) amino, aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl, 2-dimethylaminoethyl, piperidinomethyl, pyrrolidinomethyl, morpholinomethyl are preferred radicals of the group R'R''N- (CH ₂ ) _n -, where the diethylaminomethyl, piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and the amino group are particularly preferred.

The other terms used are derived from the invention definitions given here.

• (a) mindestens eine Entwicklerkomponente und
• (b) mindestens ein m-Aminophenol-Derivat gemäß Formel I und/oder dessen physiologisch verträglichen Salze,
  
  wobei
• • R¹ und R² stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder verzweigte C₁-C₈-Alkylgruppe, eine zyklische (C₃-C₈)-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine C₁-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-(C₁-C₆)-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-(C₁-C₆)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können, und m steht für eine ganze Zahl von 2 bis 6,
• • R³ steht für eine lineare oder verzweigte C₁-C₈-Alkylgruppe, eine zyklische (C₃-C₈)-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine C₁-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine Gruppe R^IIIR^IVN-(CH₂)_q-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-(C₁-C₆)-alkylgruppe, wobei R^III und R^IV gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können, und q steht für eine ganze Zahl von 2 bis 6, eine Gruppe -[(CH₂)_x-O-(CH₂)_y]m-CH₃, worin m 1 oder 2 ist, x eine ganze Zahl von 2 bis 6 und y eine ganze Zahl von 0 bis 6 ist,
• • R⁴ und R⁵ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine lineare oder verzweigte C₁-C₆-Alkylgruppe, eine Nitrogruppe, eine Carboxylgruppe, eine Cyanogruppe, eine Hydroxygruppe, eine C₁-C₆-Monohydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine Hydroxy-(C₁-C₆)-alkoxygruppe, eine Gruppe R^VR^VIN-(CH₂)_s-, worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und s steht für eine ganze Zahl von 0 bis 6,
• • n steht für eine ganze Zahl von 0 bis 6, mit der Maßgabe, dass, wenn n gleich Null ist und R³ für ein Wasserstoffatom, eine Methylgruppe oder eine 2-Hydroxyethylgruppe steht, mindestens ein Rest aus R¹, R², R⁴ und R⁵ kein Wasserstoffatom bedeutet.

A second object of the invention is an agent for dyeing keratin-containing fibers, in particular human hair, containing

• (a) at least one developer component and
• (b) at least one m-aminophenol derivative according to formula I and / or its physiologically tolerable salts,
  
  in which
• R ¹ and R ² independently of one another represent a hydrogen atom, a linear or branched C ₁ -C ₈ -alkyl group, a cyclic (C ₃ -C ₈ ) -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group , an aryl (C ₁ -C ₆ ) alkyl group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy (C ₁ -C ₆ ) alkyl group , a group R ^I R ^{II is} N- (CH ₂ ) _m -, in which R ^I and R ^II independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl- (C ₁ -C ₆ ) -alkyl group, where R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring, and m stands for an integer from 2 to 6,
• R ³ represents a linear or branched C ₁ -C ₈ -alkyl group, a cyclic (C ₃ -C ₈ ) -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an aryl- (C ₁ - C ₆ ) alkyl group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a group R ^III R ^IV N- (CH ₂ ) _q -, wherein R ^III and R ^IV are each independently Hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or an aryl (C ₁ -C ₆ ) alkyl group, wherein R ^III and R ^IV together with the nitrogen atom, a 5-, 6- or And q is an integer of 2 to 6, a group - [(CH ₂ ) _x -O- (CH ₂ ) _y ] m -CH ₃ wherein m is 1 or 2, x an integer from 2 to 6 and y is an integer from 0 to 6,
• R ⁴ and R ⁵ independently represent a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ alkyl group, a nitro group, a carboxyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a hydroxy (C ₁ -C ₆ ) alkoxy group, a group R ^V R ^VI N- (CH ₂ ) _s -, wherein R ^V and R ^VI independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and s is an integer from 0 to 6,
• N is an integer from 0 to 6, with the proviso that when n is zero and R ^{3 is} a hydrogen atom, a methyl group or a 2-hydroxyethyl group, at least one of R ¹ , R ² , R ⁴ and R ⁵ does not represent a hydrogen atom.

The preferred embodiment the agents according to the invention contain the preferred compounds of the formula I according to the first Subject of the invention.

Keratin fibers are wool, furs, feathers and especially human hair to understand. In principle, however, the colorants according to the invention can also be used for dyeing other natural fibers, such as As cotton, jute, sisal, linen or silk, modified natural fibers such. As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used.

Compositions of the invention may contain the following ingredients in the amounts indicated. developer 0.05-5% pimp 0.05-5% Surfactants, emulsifiers 0.1-20 Fatty alcohols and other emulsifiers 0.5-20 complexing 0.05-10% buffering agents 0.1-1.0 Solubilizer + solvent 0,5-15% pH adjusters upon need perfume oils 0.1-0.6% polymers 0,1-5% water 50-98%

suitable Colorant compositions are for example in DE-U1-299 11 819, DE-A-101 25 451, DE-U1-201 11 036, as well as the textbook cosmetics, ed. W. Umbach, 2nd ed. 1995, G. Thieme Verlag Stuttgart, New York described.

Next the m-aminophenol derivatives of the formula (I) contain the colorants according to the invention further at least one developer component.

When Developer components are commonly used primary aromatic amines with another, in 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 its derivatives used.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₁-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, 3-(1H-Imidazol-1-yl)propyl, 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, 3-(1H-Imidazol-1-yl)propyl, 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 may be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically acceptable salts as the developer component in the compositions according to the invention. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

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 ₁ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical containing a nitrogen-containing group, 3- (1H-imidazol-1-yl) propyl, a phenyl or a 4'-aminophenyl radical is substituted;
• G ² represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy radical (C ₁ - to C ₄ ) -alkyl radical, 3- (1H-imidazol-1-yl) -propyl, 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, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ - to C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or 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
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

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) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-) Methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

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

It can continue according to the invention be preferred as the developer component compounds in the inventive compositions which contain at least two aromatic nuclei, the substituted with amino and / or hydroxyl groups.

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 G¹² 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 dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z ¹ and Z ² independently of one another are 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 bridge Y. or is optionally part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or C ₁ - to C ₈ alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another are 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 compound for bridging Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ alkyl, with the provisos that
• The compounds of the formula (E2) contain only one bridge Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred dinuclear developing agents 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) tetramethylenediamine, N, N'-bis ( β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis (4-amino-3-methylphenyl) -ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4-amino-3-methylphenyl) -ethylenediamine; aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminopenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2, 5-diaminophenyl) -1,4,7,10-tetraoxadecane and its physiologically acceptable salts.

All particularly preferred binuclear 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, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically acceptable salts.

wobei:

• – G¹³ 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,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

Furthermore, it may be preferred according to the invention to use as the developer component in the compositions according to the invention a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

• - G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ alkyl, 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, C ₁ to C ₄ aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, C ₁ to C ₄ hydroxyalkoxy, C ₁ - to C ₄ -hydroxyalkyl- (C ₁ -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, 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, C ₁ to C ₄ aminoalkyl or C ₁ to C ₄ cyanoalkyl,
• G ¹⁵ is 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 ¹⁶ is hydrogen or a halogen atom.

The used in formula (E3) substituents are analogous 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-methylphenol, 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-methoxymethyl-phenol, 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.

All 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.

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

Farther For example, the developer component may be preferably selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196 such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (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 Patent Application JP 02019576 A2 or in the laid-open specification 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 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-one 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, G¹⁹ 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 NG¹⁷G¹⁸ und NG¹⁹G²⁰ 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 NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, if a tautomeric equilibrium exists:

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ 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 - Polyhydroxyalkylrest a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, optionally protected by an acetyl-ureide or a sulfonyl radical may be 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, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, 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, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, 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 equals 2, n has the value 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);
• When p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo(1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-S-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E4):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo (1,5-a) pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidine-S-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;

and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The Pyrazolo [1,5-a] pyrimidines of the above formula (E4) can be used as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

• – 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, 2-({3-[2-Hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[2-Hydroxyethyl)amino)-2-methoxy-5-methylphenyl}amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]ethanol 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,

sowie den physiologisch verträglichen Salzen der vorgenannten Verbindungen.The coupler components optionally additionally present in the agents according to the invention are preferably selected from

• - M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro 3-aminophenol,
• O-aminophenol and its derivatives,
• M-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 2 - ({3- [2-hydroxyethyl) amino] -4-methoxy-5- methylphenyl} amino) ethanol, 2 - ({3- [2-hydroxyethyl) amino) -2-methoxy-5-methylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol 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, for example, 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-diami no-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• Methylene dioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene,

and the physiologically acceptable salts of the aforementioned compounds.

Particularly according to the invention preferred coupler components 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-methyl, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

When Precursors of naturally-analogous dyes can be used in the compositions according to the invention In addition, indoles and indolines are used which have at least one Hydroxy or amino group, preferably as a substituent on the six-membered ring, exhibit. These groups can bear further substituents, for. B. in the form of an etherification or Esterification of the hydroxy group or alkylation of the amino group.

in der unabhängig voneinander

• – G²¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – G²² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – G²³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – G²⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-G²⁶, in der G²⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – G²⁵ steht für eine der unter G²⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula IIa,

in the independently of each other

• G ²¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• G ²² is hydrogen or a -COOH group, where the -COOH group may also be in the form of a salt with a physiologically compatible cation,
• G ²³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• - G ²⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-G ²⁶ , in which G ²⁶ is a C ₁ -C ₄ alkyl group, and
• - G ²⁵ stands for one of the groups mentioned under G ²⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

Especially noteworthy 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 in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

• – G²⁷ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – G²⁸ steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – G²⁹ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – G³⁰ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-G³², in der G³² steht für eine C₁-C₄-Alkylgruppe, und
• – G³¹ steht für eine der unter G³⁰ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula IIb,

in the independently of each other

• G ²⁷ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• - G ²⁸ is hydrogen or a -COOH group, wherein the -COOH group is also used as a salt with a physiologically compatible cation may be present
• G ²⁹ is hydrogen or a C ₁ -C ₄ -alkyl group,
• G ³⁰ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-G ³² , in which G ³² is a C ₁ -C ₄ -alkyl group, and
• - G ³¹ stands for one of the groups mentioned in G ³⁰ ,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially 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 of 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 the 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. The hydrochlorides, the sulfates and hydrobromides used. The indole or Indoline derivatives are common in these in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment contain the colorants of the invention for further modification of the shades in addition to the present invention Compounds additionally common directing Dyes, such as nitrophenylenediamines, nitroaminophenols, azo dyes, Anthraquinones or indophenols. Preferred substantive dyes are those under 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 as well as 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-hydroxyethyl) 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 may preferably contain a cationic substantive dye. Particularly preferred are

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called.

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

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of group (c). The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention particularly preferred substantive dyes.

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

Farther can the preparations according to the invention also occurring in nature dyes, as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alkano root are included.

It is not required that the in the inventive compositions contained oxidation dye precursors or the optionally contained direct dyes each represent uniform compounds. Rather, you can in the colorants according to the invention, due to the production process for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, eg. B. toxicological, must be excluded.

Regarding the in the hair dyeing and -tönungsmitteln applicable dyes is still expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; Dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology" (ed. Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", issued by the European Community, available in diskette form from the German Association of Industrial and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim.

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

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x -CH₂-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 surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present 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 having 2 or 3 C 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 having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 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 having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids having 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 having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 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.

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

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - C _{1 2} -C ₂₂ fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol,
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. 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 one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting 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 particular work-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 C₁₂- bis C_{1 6}-Alkylgruppen besteht.

Particular preference is given to those alkylpolyglycosides in which R ¹

• Consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• Essentially C _{1 2} and C _{1 4} -alkyl groups,
• - essentially of C ₈ - to C _{1 6} alkyl, or
• - essentially of C ₁₂ - to C ₆ -alkyl groups is _1.

When Sugar component Z can any mono- or oligosaccharides are used. Usually Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Such sugars are, for example, glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, Gulose, idose, talose and sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The usable according to the invention Alkyl polyglycosides contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x 1.1 to 1.4.

The Alkyl glycosides can in addition to their surfactant effect also serve the fixation of fragrance components to improve on the hair. The person skilled in the art will therefore be that one over the effect of the perfume oil beyond the duration of the hair treatment the hair desired is, preferably to this class of substance as a further ingredient the preparations according to the invention To fall back on.

Also The alkoxylated homologs of said alkyl polyglycosides can be used according to the invention become. These homologs can 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 cosurfactants. Zwitterionic surfactants are surface-active compounds which carry 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 N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, apart from a C ₈ to C _{1 8} alkyl or acyl group in the molecule ₃ H group containing at least one free amino group and at least one -COOH or -SO and which are capable of forming inner 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 having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention can as cationic surfactants, especially those of the quaternary ammonium compound type, the esterquats and amidoamines are used.

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

Esterquats 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 marketed under the brands Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a 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 prepared 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 brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine is.

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

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), 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".

at it may be the compounds with alkyl groups used as surfactant each are uniform substances. It is, however, in usually preferred in the preparation of these substances by native to go out with vegetable or animal raw materials, so that one Substance mixtures with different, from the respective raw material dependent alkyl chain lengths receives.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions are obtained when, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or -alkoholate be used as catalysts. The usage of products with restricted homolog distribution may be preferred be.

• – 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-Dimethyldiallylammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-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 Polyacrylsäuren, 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, Cellu lose-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,
• – Antischuppenwirkstoffe 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 H,
• – 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 Penetrationsstoffe 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 Wasserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

enthalten.Furthermore, the colorants according to the invention further active ingredients, auxiliaries and additives, such as

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• 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 polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / croton 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, cellulosic derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, 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 soya lecithin, egg lecithin and cephalins,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, 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 staining 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, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic 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 extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing 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,
• - antioxidants,

contain.

Regarding further optional components as well as the amounts of these components used expressly on the specialist manuals known to those skilled in the art, eg. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

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

For the purposes of the present invention, aqueous-alcoholic solutions are aqueous solutions containing 3 to 70 wt .-% of a C ₁ -C ₄ alcohol, in particular ethanol or isopropanol to understand. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

The actual oxidative staining the fibers can basically done with atmospheric oxygen. However, preference is given to a chemical Oxidizing agent used, especially if in addition to the coloring, a whitening effect desired on human hair is. The oxidizing agents are persulfates, chlorites and in particular Hydrogen peroxide or its addition products to urea, Melamine and sodium borate in question. However, according to the invention the oxidation colorant also be applied to the hair together with a catalyst, the oxidation of the dye precursors, e.g. by 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+. Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle 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, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

• – 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 include peroxidases, which can significantly enhance 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 aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

• Pyranose oxidase and eg D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol 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.

One third subject of the invention is a process for dyeing keratin-containing fibers, in particular human hair, wherein a colorant of the second article of the invention to the keratin-containing fibers upset, some time, usually About 15-30 minutes, left on the fiber and then again rinsed or washed out with a shampoo.

The actual hair dye is expediently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the dye precursors, produced. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Especially the use of the hair dye in a weakly alkaline is preferred Milieu. The application temperatures can be in a range between 15 and 40 ° C lie. After an exposure time of usually 5 to 45 minutes becomes the hair dye by rinsing of which to be colored Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, e.g. a dyeing shampoo, has been used.

Especially in hard-to-dye Hair can be the preparation with the dye precursors as well without prior mixing with the oxidation component on the Hair will be applied. After an exposure time of 20 to 30 minutes will then - if necessary after an intermediate rinse - the oxidation component applied. After another exposure time of 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors to effect a better penetration into the hair, the corresponding Medium adjusted to a pH of about 4 to 7. According to one second variant is first an air oxidation, with the applied agent being preferred has a pH of 7 to 10. At the subsequent accelerated Post-oxidation may be the use of acidified peroxydisulfate solutions as Oxidizing agent may be preferred.

One fourth subject of the invention is the use of the compounds the first object for dyeing keratin-containing fibers, especially human hair.

One fifth The invention relates to the use of the agent of the second Subject of the invention for dyeing keratin-containing fibers, especially human hair.

example 1

1.1 Preparation of 5-amino-2- [2- (2-methoxyethoxy) ethoxy] phenol, Hydrochloride (K1)

The Substance can be analogous to the following two-step reaction sequence starting from 3,4-methylenedioxynitrobenzene and diethylene glycol monomethyl ether are shown:

1st stage: presentation of 2- [2- (2-methoxyethoxy) ethoxy] -5-nitrophenol

18.0 g (0.272 mol) of potassium hydroxide are dissolved in 200 ml of diethylene glycol monomethyl ether, then 25.0 g (0.147 mol) of 3,4-methylenedioxynitrobenzene are added and the reaction mixture is heated at 110 ° C. for 3 hours. After cooling, it is poured into about 500 ml of ice water and the resulting solid is filtered off with suction. The filtrate is brought to pH 4-5 with concentrated hydrochloric acid and allowed to stand in the refrigerator for approximately 12 hours. The solid formed after this time is filtered off with suction and washed with water. The product can be used after drying without further purification in the second stage.
Yield: 30.0 g (80%)
Melting point .: 79-82 ° C
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 3.24 (s, 3H); 3.49 (t, 2H); 3.64 (t, 2H), 3.81 (t, 2H); 4.28 (t, 2H); 7.11 (arom., D, 1H); 7.67 (arom. D, 1H); 7.72 (arom., Dd, 1H); 10.03 (br., OH)

2nd stage: presentation of 5-amino-2- [2- (2-methoxyethoxy) ethoxy] phenol, hydrochloride

There are 30.8 g (0.120 mol) of 5-nitro-2- [2- (2-methoxyethoxy) ethoxy] phenol from step 1 dissolved in 400 ml of ethanol. After the addition of the hydrogenation catalyst (5% Pd / C) is hydrogenated at atmospheric pressure until the theoretical hydrogen uptake. Then, the catalyst is filtered off and the reaction mixture is poured into a mixture of 15 ml of hydrochloric acid (conc.) And 20 ml of ethanol. The solvent is removed on a rotary evaporator and the residue is dried.
Yield: 28.3 g (90%)
Melting point: 122-123 ° C
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 3.24 (s, 3H); 3.48 (t, 2H); 3.59 (t, 2H), 3.71 (t, 2H); 4.10 (t, 2H); 6.78 (arom., Dd, 1H); 6.91 (arom. D, 1H); 6.98 (arom., D, 1H); 9.70 (br., OH); 10.09 (br., NH ₂ )

1.2 Coloring of 5-Amino-2- [2- (2-methoxyethoxy) ethoxy] phenol, hydrochloride (K1) strands of hair

For the preparation of the staining 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® ^® techn. 4.0% by weight Texapon.RTM ^® 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 (see Table 1 or Table 2) suspended in distilled water or dissolved by heating. Subsequently, ammonia (<1 mL, 25% ammonia solution) was added until the pH was between 9 and 10.

The dissolved Dye precursors were added sequentially to the hot cream incorporated. Subsequently was made up to 97 g with distilled water and adjusted to pH 9.5 with ammonia. To Fill up with distilled water to 100 g, the mixture was stirred cold (<30 ° C), wherein a homogeneous cream was created.

For the colorations were 25g of the dye cream with 25 g of an aqueous 6% hydrogen peroxide solution added.

One strand of hair (80% gray, 330 mg to 370 mg heavy) was added to each of the mixtures thus obtained. Subsequently, the mixtures and the hair strands were placed on a watch glass and the hair strands well embedded. After 30 minutes contact time at room temperature, the hair swatches were removed and mixed with an aqueous solution Texapon ^® EVR washed so often until the excess color was removed. The strands of hair were dried in the air.

K1:

5-Amino-2-[2-(2-methoxyethoxy)ethoxy]phenol, Hydrochlorid

The results obtained in the staining tests are listed in the following table. Table 1:

K1:

5-Amino-2- [2- (2-methoxyethoxy) ethoxy] phenol, hydrochloride

Example 2

2.1 Preparation of 5-amino-2- (2-isopropoxyethoxy) phenol, Hydrochloride (K2)

The Substance can be analogous to the following two-step reaction sequence starting from 3,4-methylenedioxynitrobenzene and 2-isopropoxyethanol are shown:

1st stage: presentation of 2- (2-isopropoxyethoxy) -5-nitrophenol

In 200 ml of 2-isopropoxyethanol 15.2 g (0.272 mol) of potassium hydroxide are dissolved, then 25.0 g (0.147 mol) of 3,4-methylenedioxynitrobenzene are added and the reaction mixture is heated to 110 ° C for 3 hours. After cooling, it is poured into about 500 ml of ice water and the resulting solid is filtered off with suction. The filtrate is brought to pH 4-5 with concentrated hydrochloric acid and allowed to stand for approximately 12 hours in the freezer at -18 ° C. The solid formed after this time is filtered off with suction and washed several times with water. The product can be used after drying without further purification in the second stage.
Yield: 28.9 g (80%)
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 1.11 (d, 6H); 3.68 (sep, 1H); 3.82 (t, 2H), 4.20 (t, 2H); 7.13 (d, 1H); 7.78 (s, 1H); 7.87 (d, 1H)

2nd stage: presentation of 5-amino-2- (2-isopropoxyethoxy) phenol, hydrochloride

There are 28.0 g (0.116 mol) of 2- (2-isopropoxyethoxy) -5-nitrophenol from step 1 dissolved in 400 ml of ethanol. After the addition of the hydrogenation catalyst (5% Pd / C) is hydrogenated at atmospheric pressure until the theoretical hydrogen uptake. The catalyst is then filtered off and the reaction mixture is poured into a mixture of 10 ml of hydrochloric acid (conc.) And 20 ml of ethanol. The solvent is removed on a rotary evaporator and the residue is dried.
Yield: 21.5 g (75%)
Melting point: 112-115 ° C
¹ H-NMR (400 MHz, D ₂ O): δ = 1.20 (d, 6H); 3.85 (sep, 1H); 3.90 (t, 2H), 4.23 (t, 2H); 6.91 (d, 1H); 6.95 (s, 1H); 7,11 (d, 1H)

2.2 Coloring of 5-amino-2- (2-isopropoxyethoxy) phenol, hydrochloride (K2) on strands of hair

K2:

5-Amino-2-(2-isopropoxyethoxy)phenol, Hydrochlorid

The experiment is carried out as described in section 1.2. The staining results are summarized in the table below. Table 2:

K2:

5-amino-2- (2-isopropoxyethoxy) phenol, hydrochloride

Claims (13)

Compounds according to formula I and its physiologically acceptable salts,

wherein R ¹ and R ² independently represent a hydrogen atom, a linear or branched C ₁ -C ₈ alkyl group, a cyclic (C ₃ -C ₈ ) alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group , an aryl (C ₁ -C ₆ ) alkyl group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy (C ₁ -C ₆ ) alkyl group , a group R ^I R ^{II is} N- (CH ₂ ) m -, in which R ^I and R ^II independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl- (C ₁ -C ₆ ) -alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring, and m is an integer from 2 to 6, R ³ is a linear or branched C ₁ -C ₈ alkyl group, a cyclic (C ₃ -C ₈ ) alkyl group, a C ₂ -C ₆ -Al kenyl group, an optionally substituted aryl group, an aryl (C ₁ -C ₆ ) alkyl group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a group R ^III R ^IV N- (CH ₂ ) _q -, in which R ^III and R ^IV independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl- (C ₁ -C ₆ ) -alkyl group, where R ^III and R ^IV together with the nitrogen atom can form a 5-, 6- or 7-membered ring, and q is an integer from 2 to 6, a group - [(CH ₂ ) _x -O- (CH ₂ ) y ] _m -CH ₃ , wherein m is 1 or 2, x is an integer of 2 to 6 and y is an integer of 0 to 6, R ⁴ and R ⁵ are independently a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ alkyl group, a cyclic (C ₃ -C ₈ ) alkyl group, a nitro group, a carboxyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydrox yalkyl group, a C ₁ -C ₆ alkoxy group, a hydroxy (C ₁ -C ₆ ) alkoxy group, a group R ^V R ^VI N- (CH ₂ ) _s -, wherein R ^V and R ^VI are each independently A hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or an aryl C ₁ -C ₆ alkyl group, and s represents an integer of 0 to 6, n represents an integer of 0 to 6, provided that when n is zero and R ^{3 is} a hydrogen atom, a methyl group or a 2-hydroxyethyl group, at least one of R ¹ , R ² , R ⁴ and R ⁵ does not represent a hydrogen atom. Compounds according to claim 1, characterized that in Formula I n for 0 or 1 stands. Compounds according to one of claims 1 or 2, characterized in that in formula IR ^{1 is} a hydrogen atom and R ^{2 is} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -monohydroxyalkyl group and a C ₂ - C ₆ polyhydroxyalkyl group. Compounds according to one of claims 1 to 3, characterized in that in formula IR ^{3 is} a linear or branched C ₃ -C ₈ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group or a group - [(CH ₂ ) _x -O- (CH ₂ ) _y ] _m -CH ₃ , wherein m is 1 or 2, x is an integer from 2 to 6 and y is an integer from 0 to 6. Compounds according to claim 1, selected from the group formed from 5-amino-2- (2- (2-methoxyethoxy) ethoxy] phenol, 5-amino-2- (2-isopropoxyethoxy) phenol, 5-amino-2- (2-phenoxyethoxy) phenol, 2- (2-isopropoxyethoxy) -5- (methylamino) phenol, 5 - [(2-hydroxyethyl) amino] -2- (2-isopropoxyethoxy) phenol, 5 - [(2-hydroxyethyl) amino] -2- [2- (2-methoxyethoxy) ethoxy] phenol, 2- [2- (2-methoxyethoxy) ethoxy] -5- (methylamino) phenol, 5- (methylamino) -2- (2-phenoxyethoxy) phenol, 5 - [(2-hydroxyethyl) amino] -2- (2-phenoxyethoxy) phenol and the salts of the aforementioned compounds. Dyeing agent keratin-containing fibers containing (a) at least one developer component and (B) at least one compound according to any one of claims 1 to 5th Means according to claim 6, characterized in that it is at least a direct dye, preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant contains. Agent according to one of claims 6 or 7, characterized that it at least one additional one Coupler component contains as oxidation dye precursor. Agent according to one of claims 6 to 8, characterized in that it contains oxidizing agent, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution. Agent according to one of claims 6 to 9, characterized that it contains anionic, zwitterionic or nonionic surfactants. Use of at least one compound according to one the claims 1 to 5 for dyeing keratin-containing fibers. Use of at least one agent according to one the claims 6 to 10 for dyeing keratin-containing fibers. Dyeing process keratin-containing fibers, in particular human hair, in which a colorant, according to one the claims 6 to 10 applied to the keratinous fibers, some time, usually About 15-30 minutes, left on the fiber and then again rinsed or washed out with a shampoo.