DE102006042227A1 - Reduction of hair aging - Google Patents

Abstract

The programmed cell death (apoptosis) of hair follicle cells is promoted or prematurely induced by stress factors, in particular in the context of an oxidative hair treatment. The use of quantized beta-hydroxybutyric acid derivatives protects the hair from premature apoptosis of the follicular cells.

Description

The The present invention relates to the use of quaternized beta-hydroxybutyric acid derivatives for compensation hair age-induced premature aging or dying of hair.

Human Hair is becoming more diverse today Treated with hair cosmetic preparations. These include about Cleaning hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and deforming the hair with bleaches, dyes, tints, waving agents and styling preparations. There are funds for change the color of the hair, as well as the deformation of the hair an outstanding Role.

Apart from the color-modifying blonding agents, which cause an oxidative lightening of the hair by degradation of the natural hair dyes, so in the field of hair coloring essentially four types of hair dye are of importance:
For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such hairline colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings but usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.

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-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-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -diaminopropan-2-ol.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols used. Particularly suitable coupling agents are 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

For temporary dyeings become common dyeing or tinting agent used as dyeing Component so-called direct pullers included. This is it about dye molecules, which grow directly on the hair and no oxidative process to training need the color. Belongs to these dyes for example, that from ancient times to the coloring of body and hairs known henna. These dyes are against shampooing usually much more sensitive than oxidative stains, so that then much more quickly a much undesirable nuance shift or even a visible "discoloration" occurs.

Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. Such a process with 5,6-dihydroxyindoline as a dye precursor has been described in US Pat EP-B1-530 229 described. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The dyeing can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. For use in individuals with originally red and especially dark to black hair color can satisfy de results often only by the concomitant use of other dye components, in particular special oxidation dye precursors can be achieved.

• A Verbindungen, die eine reaktive Carbonylgruppe enthalten mit Komponente
• B Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen und (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen

enthalten. Die entsprechende Färbemethode (im folgenden Oxofärbung genannt) wird beispielsweise in den Druckschriften WO-A1-99/18916 , WO-A1-00/38638 , WO-A1-01/34106 und WO-A1-01/47483 beschrieben. Die resultierenden Färbungen besitzen teilweise Farbechtheiten auf der keratinhaltigen Faser, die mit denen der Oxidationsfärbung vergleichbar sind. Das mit der schonenden Oxofärbung erzielbare Nuancenspektrum ist sehr breit und die erhaltene Färbung weist oftmals eine akzeptable Brillanz und Farbtiefe auf. Die vorgenannten Komponenten A und B, im weiteren als Oxofarbstoffvorprodukte bezeichnet, sind im allgemeinen selbst keine Farbstoffe, und eignen sich daher jede für sich genommen allein nicht zur Färbung keratinhaltiger Fasern. In Kombination bilden sie in einem nichtoxidativen Prozess Farbstoffe aus. Unter Verbindungen der Komponente B können allerdings auch entsprechende Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kupplertyp mit oder ohne Einsatz eines Oxidationsmittels Verwendung finden. Somit läßt sich die Methode der Oxofärbung ohne weiteres mit dem oxidativen Färbesystem kombinieren.One way to stain keratinous fibers is to use stains that contain a combination of component

• A compounds containing a reactive carbonyl group with component
• B Compounds selected from (a) CH-acidic compounds and (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds

contain. The corresponding dyeing method (referred to below as oxo dyeing) is described, for example, in the publications WO-A1-99 / 18916 . WO-A1-00 / 38638 . WO-A1-01 / 34106 and WO-A1-01 / 47483 described. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing. The Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth. The aforementioned components A and B, hereinafter referred to as Oxofarbstoffvorprodukte, are generally not themselves dyes, and are therefore each alone taken not for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent under compounds of component B. Thus, the oxo staining method can be readily combined with the oxidative staining system.

It is a general endeavor that can be achieved with the known methods colorations to intensify in your color result. That way either achieved with the same amount of dye a more intense color be, or leave it while preserving dyes, a desired degree of intensity coloring maintained. The latter carries also to the economics of colorants. Furthermore, should scored dyeings a high level of Color fastness e.g. have against washing, light or friction and have to Especially in the context of hair care compatible with other hair treatment products be. Especially, especially the oxidative color-change agents, spare the hair structure.

gespalten und auf diese Weise eine Erweichung der Keratinfaser erreicht. Hydrogensulfit-, sulfit- bzw. disulfithaltige Reduktionsmittel weisen nicht den starken Eigengeruch der merkaptanhaltigen Mittel auf. Die Spaltung kann wie zuvor geschildert in einem Fixierschritt mit Hilfe eines Oxidationsmittels unter Bildung von neuen Disulfid-Brücken wieder rückgängig gemacht werden.A permanent deformation keratinhaltiger fibers is usually carried out by mechanically deforming the fiber and determines the deformation by suitable means. Before and / or after this deformation, the fiber is treated with a keratin-reducing preparation. After a rinsing process, the fiber is then treated with an oxidizing agent preparation, rinsed and freed from the deformation aids (winders, papillots). When a mercaptan, eg, ammonium thioglycolate, is used as the keratin-reducing component, it splits a part of the disulfide bridges of the Kerstin molecule into -SH groups, so that softening of the keratin fiber occurs. In the subsequent oxidative fixation again disulfide bridges are knotted in the hair keratin, so that the Keratingefüge is fixed in the predetermined deformation. Alternatively, it is known to use sulfite instead of the mercaptans for hair styling. By bisulfite solutions and / or sulfite solutions and / or disulfite solutions, disulfide bridges of keratin in a sulfitolysis according to the equation

split and achieved in this way a softening of the keratin fibers. Hydrogen sulfite, sulfite or disulfite containing reducing agents do not have the strong odor of the mercaptan-containing agents. The cleavage can be reversed as described above in a fixing step using an oxidizing agent to form new disulfide bridges.

It was now surprisingly found that the topical, cosmetic treatment of hair with quaternized beta-hydroxybutyric acid derivatives hair Metabolism of the hair towards stress factors, such as. oxidative stress, keeps in balance and preventing the premature aging or premature death of hair (anti-aging) as part of a cosmetic hair treatment causes.

Without to want to commit to a mechanism of action, revealed the latest Investigations by the applicant that during hair treatment, in particular through the influence of Oxidizing agents, e.g. of peroxides, the energy balance of Hair root (hair follicle) is lowered. The energy budget the hair follicle is represented by the content of adenosine 5'-triphosphate (ATP). ATP deficiency in the cells of the hair follicle may be after knowledge of the Applicant to a shortened Life cycle of the hair and at worst to the death of the Follicle cell lead.

In addition, the apoptosis of the hair follicle cells, ie the programmed cell death of the hair follicle cells can be promoted by the action of oxidant-containing cosmetics as a stress factor. The programmed cell death first manifests itself in morphological changes such as the shrinkage of the cells. Furthermore, a fragmentation of the chromosomal DNA shows up and it ultimately comes to the death and degradation of the affected cells. In contrast to the other major mechanism of cell death, necrosis, apoptosis is actively performed by the cell itself and is part of the metabolism of the cell. As a result, this form of cell death is subject to strict control and it is ensured that the cell in question is destroyed without damaging the neighboring tissue. The triggers of apoptosis are intrinsic or extrinsic signals, such as tumor necrosis factor alpha (TNF), so-called "death factors" or genotoxic substances, and central regulators of apoptosis are caspases belonging to the family of cysteine proteases or the antagonists Bax and Bcl This group of proteins, commonly referred to as the Bcl-2 family, can be divided into two groups, an anti-apoptotic (Bcl-2, Bcl-xL, Bcl-w, Mcl-1, etc.) and a pro-apoptotic (Bax, Bak, Bad, Bcl-xS, Bik, Bid) where Bax and Bcl-2 represent the two main representatives (a review of apoptotic processes in the cell can be found in 1 ). Usually both groups are in equilibrium. If the ratio of Bax and Bcl-2 shifts, there are changes in the cell. For example, the increased expression of Bax leads to increased apoptosis.

in the Hair follicle, so in the biologically active part of the hair plays Apoptosis, especially in the hair cycle, plays a role in the regression phase of the follicle, the subsequent Resting phase and rejection hair that initiates apoptosis. Also in Hair follicle, apoptosis is controlled by various factors, among others TGFb1 (transforming growth factor beta 1), Bax / Bcl2 or different caspases play a role. In addition to the naturally occurring Apoptosis in the regular Hair cycle of humans, apoptosis is also still related discussed with increased hair loss. Various triggers (hereditary conditional, stressors etc.) in the hair follicle to reinforced Lead to apoptosis and thus the regression phase and thus ultimately the ejection hair premature initiated.

Also oxidative stress can cause apoptosis in cells. Especially Cyclooxygenase-2 (Cox2) plays a role in this process as a mediator Role. Hair follicles also discuss the effects of oxidative stress, e.g. as cause for the hair graying, as oxidative stress to apoptosis in the hair follicle melanocytes to lead can. Further effects of oxidative stress, especially in Hair follicles have not been studied yet, but there are none Evidence that the hair follicle has a special protection mechanism features, him from stress factors, such as oxidative stress, protects, so that it can be assumed that the biologically active Hair follicle cells, like other cells, due to oxidative stress damaged can be.

The Applicant has now surprisingly found that by using quaternized beta-hydroxybutyric acid derivatives the hair follicle cells from premature apoptosis, initiated by Stress factors, such as oxidative stress, UV radiation, Aging processes, stress due to a non-physiological pH, protected become. The protection against oxidative stress occurs even during the oxidative hair treatment.

worin
R¹, R² und R³ unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₄-Hydroxyalkylgruppe stehen,
R⁴ ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₆-Acylgruppe bedeutet,
R⁵ für ein Wasserstoffatom, eine negative Ladung oder eine C₁- bis C₄-Alkylgruppe steht,
zum Schutz des Haars, insbesondere der Haarfollikelzellen, vor Stressfaktoren.A first subject of the invention is therefore the cosmetic use of at least one compound according to formula (I)

wherein
R ¹ , R ² and R ³ independently of one another represent a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group,
R ⁴ denotes a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₆ -acyl group,
R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group,
for the protection of hair, in particular hair follicle cells, from stress factors.

Stress factors are within the meaning of the inventions such internal or external factors or stimuli that induce premature apoptosis.

The Effect of stress factors (such as the effect of the oxidative Stresses, (caused for example by free radicals), stress by UV radiation, stress by aging processes, mental Stress or stress due to non-physiological pH values) on the Metabolism of hair or hair follicle cells, is caused by the use according to the invention prevented or diminished. In the process, it is caused by stress factors favored or accelerated apoptosis of the hair follicle cells prevented or reduced. The premature death due to stress factors of the hair or the premature failure of the hair becomes this way prevented or diminished.

The Compounds of the formula (I) preferably have a molecular weight of less than 500 g / mol, more preferably less than 400 g / mol.

The Cosmetic treatment is preferably by topical application cosmetic agent containing at least one compound according to formula (I) included.

In formula (I), the radicals R ¹ , R ² and R ^{3 are} preferably, independently of one another, a methyl or an ethyl group, particularly preferably a methyl group.

The radical R ⁴ is preferably a hydrogen atom or a C ₂ to C ₄ acyl group. A preferred C ₂ to C ₄ acyl group is the acetyl group.

When R ^{5 is} a negative charge, the compounds of formula (I) are in the form of an inner salt. When R ^{5 is} a hydrogen atom or a C ₁ - to C ₄ -alkyl group, the compound of the formula (I) is in the form of a salt with a physiologically tolerable anion X ^- as the counterion. Active principle according to the invention is the structural unit of the formula (I).

By definition, the physiologically acceptable anions X ^- may not only carry a negative charge but may also have a charge number greater than one. In the latter case, the anions X ^{- of} the salt form are described for maintaining electroneutrality by formulating a stoichiometric coefficient of less than 1 before the name of the anion. The physiologically acceptable anions are preferably selected from halide, 0.5 sulfate, hydrogen sulfate, 0.5 carbonate, bicarbonate, 1/3 phosphate, 0.5 hydrogen phosphate, dihydrogen phosphate, carboxylate, such as lactate, citrate or tartrate. Particularly preferably, X ^- is chloride, bromide or a carboxylate counter ion, especially lactate, citrate or tartrate.

The beta carbon atom of Buttersäuregrundgerüsts the Compounds of formula (I) is chiral. The object of the invention relates both to compounds of formula (I) in L-configuration, as well as compounds of formula (I) in D configuration and mixtures both configurations, such as Racemate.

Examples of a (C ₂ - to C ₄ ) -hydroxyalkyl group of the formula (I) are 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and 4-hydroxybutyl.

Examples of a (C ₁ - to C ₄ ) -alkyl group of the formula (I) are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Examples of a (C ₂ - to C ₅ ) -acyl group of the formula (I) are acetyl, propionyl, butyryl and valeryl.

Prefers is the compound used according to the invention according to formula (I) at least one compound selected from the group L-carnitine, D-carnitine, D, L-carnitine, L-carnitine tartrate, D-carnitine tartrate, D, L-carnitine tartrate, L-carnitine lactate, D-carnitine lactate, D, L-carnitine lactate, L-carnitine citrate, D-carnitine citrate, D, L-carnitine citrate, L-acetylcarnitine, D-acetylcarnitine and D, L-acetylcarnitine.

• i) vor, während oder im Anschluß an eine oxidative Haarbehandlung und/oder
• ii) vor, während bzw. im Anschluß an eine Haarbehandlung bei nicht physiologischen pH-Werten, insbesondere von pH-Werten größer pH 7,4, insbesondere größer pH 8, statt.

The use according to the invention of the compounds of the formula (I) according to the first subject of the invention is preferred

• i) before, during or after an oxidative hair treatment and / or
• ii) before, during or after a hair treatment at non-physiological pH values, in particular of pH values greater than pH 7.4, in particular greater than pH 8, instead of.

Of the physiological pH is by definition in a pH range of pH 7.4 to 5.5.

The Feature "im Connection "to a hair treatment means at intervals of up to 12 hours, preferably directly following said Hair treatment. The feature "before" the hair treatment means at intervals of up to 12 hours before, preferably directly before.

The Use of the first subject of the invention is not therapeutic.

worin
R¹, R² und R³ unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₄-Hydroxyalkylgruppe stehen,
R⁴ ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₆-Acylgruppe bedeutet,
R⁵ für ein Wasserstoffatom, eine negative Ladung oder eine C₁- bis C₄-Alkylgruppe steht,
zur Herstellung eines Mittels zum Schutze des Haars, insbesondere der Haarfollikelzellen, vor Stressfaktoren.A second object of the invention is the use of at least one compound according to formula (I),

wherein
R ¹ , R ² and R ³ independently of one another represent a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group,
R ⁴ denotes a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₆ -acyl group,
R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group,
for the preparation of an agent for protecting the hair, in particular the hair follicle cells, from stress factors.

worin
R¹, R² und R³ unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₄-Hydroxyalkylgruppe stehen,
R⁴ ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₆-Acylgruppe bedeutet,
R⁵ für ein Wasserstoffatom, eine negative Ladung oder eine C₁- bis C₄-Alkylgruppe steht,
zur Herstellung eines Mittels zum Schutze vor durch Stressfaktoren begünstigten, vorzeitigem Haarausfall.A third object of the invention is the use of at least one compound according to formula (I),

wherein
R ¹ , R ² and R ³ independently of one another represent a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group,
R ⁴ denotes a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₆ -acyl group,
R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group,
for the preparation of an agent for protection from premature alopecia favored by stressors.

When Preferred compounds of formula (I) apply in both embodiments two and three mutatis mutandis the corresponding embodiments of the first subject of the invention.

In the following, the preferred embodiments of the prepared in the context of the inventive use means for protecting the hair from oxidative stress or to protect against the premature death of the hair or to protect against premature hair loss are further characterized:
The compounds of the formula (I) are preferably in an amount of 0.001 to 10 wt .-%, particularly preferably from 0.01 to 5 wt .-%, most preferably from 0.1 to 2 wt .-%, respectively based on the weight of the ready-to-use agent, contained in the funds.

In a preferred embodiment as a colorant contain the funds additionally at least one color-changing Component.

• (a) aus mindestens einem Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens einer Kupplerkomponente und/oder
• (b) aus Oxofarbstoffvorprodukten und/oder
• (c) aus mindestens einem direktziehenden Farbstoff und/oder
• (d) aus mindestens einer Vorstufe naturanaloger Farbstoffe und/oder
• (e) aus mindestens einem Oxidationsmittel und gegebenenfalls zusätzlich mindestens einem Bleichverstärker.

The color-changing component is preferably selected

• (A) from at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or
• (b) from oxo dye precursors and / or
• (c) from at least one direct dye and / or
• (D) from at least one precursor of natural dyes and / or
• (E) from at least one oxidizing agent and optionally additionally at least one bleach booster.

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

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (Ent1)

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (C ₁ -C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• - G ² represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C4-monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C _{1 to} C ₄ ) alkyl or C ₁ to C ₄ alkyl substituted with 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.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (Ent1) are in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, C ₁ to C ₄ monohydroxyalkylamino groups, Imidazolinium and ammonium.

Especially preferred p-phenylenediamines of the formula (Ent1) 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-para-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 and 5,8-diaminobenzo-1,4-dioxane as well their physiologically compatible Salt.

Very particularly preferred according to the invention p-phenylenediamine derivatives of the formula (Ent1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-pheny lendiamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

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

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁-bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und 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 (Ent2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (Ent2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

Among the binuclear developer components that can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (Ent2) 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 are each independently 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 -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 formula (Ent2) contain only one bridge Y per molecule and
• - The compounds of formula (Ent2) contain at least one amino group which carries at least one hydrogen atom.

The substituents used in formula (Ent2) are analogous according to the invention to the above statements Are defined.

preferred binuclear developer components of the formula (Ent2) 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, 1,3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically tolerable Salts.

All particularly preferred binuclear developer components of the formula (Ent2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis- (2-hydroxy-5-aminophenyl) methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of 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 a p-aminophenol derivative or one of its physiologically tolerable salts. Particularly preferred are p-aminophe nol derivatives of the formula (Ent3)

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 Substituents used in formula (Ent3) are analogous to the invention to the above statements Are defined.

preferred p-aminophenols of the formula (Ent3) 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- (diethyl-aminomethyl) -phenol and its physiological acceptable Salts.

All particularly preferred compounds of the formula (Ent3) 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 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-methoxypyridine 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 published patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969 . WO 94/08970 . EP-740 931 and DE 195 43 988 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-hydrazino pyrazole, 1-Ben Cyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5- Diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4 , 5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl 1-isopropylpyrazole, 4-amino-5- (2-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 belogen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

Preferred pyrazolopyrimidine derivatives are in particular the derivatives of pyrazolo [1,5-a] opyrimidine of the following formula (Ent4) and its tautomeric forms, provided that 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, where 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 lie at positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The Substituents used in formula (Ent4) are analogous according to the invention to the above statements Are defined.

Unter den Pyrazolo[1,5-a]pyrimidinen der obenstehenden Formel (Ent4) kann man insbesondere nennen:

• – 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-5-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.When the pyrazolo [1,5-a] pyrimidine of the above formula (Ent4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

Among the pyrazolo [1,5-a] pyrimidines of the above formula (Ent4) may be mentioned in particular:

• - 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] pyrimidin-5-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-hydroxyethyl) 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 (Ent4) can be used as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives and heterocyclic compounds used.

• – 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-Diaminophenoxy-ethanol, 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-[(2-Hydroxyethyl)amino]-4,5-dimethylphenyl}-amino)ethanol, 2-[3-Morpholin-4-ylphenyl)amino]ethanol, 3-Amino-4-(2-methoxyethoxy)-5-methylphenylamin 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-Amino-benzomorpholin,
• – 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 deren physiologisch verträglichen Salze.

According to preferred coupler components are

• - M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro 3-aminophenol,
• O-aminophenol and its derivatives,
• - M-Diaminobenzene and its derivatives such as 2,4-diaminophenoxy-ethanol, 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 - [( 2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine 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-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylendioxybenzolderivate such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.

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-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically tolerable Salts of the aforementioned compounds.

The Agents preferably contain the developer components in an amount from 0.005 to 10% by weight, preferably from 0.1 to 5 wt .-%, each based on the total agent.

The Means contain the coupler components preferably in an amount from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, respectively based on the total mean.

• A Verbindungen, die eine reaktive Carbonylgruppe enthalten mit mindestens einer Verbindung der Komponente
• B Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen

enthalten.The agent can be used as color-modifying component in the form of Oxofarbstoffvorprodukte at least one combination of at least one compound of the component

• A compounds containing a reactive carbonyl group with at least one compound of the component
• B compounds selected from (a) CH-acidic compounds, (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds

contain.

• a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Kondensationsverbindung
• b) Alkoholen unter Bildung von Acetalen oder Ketalen als Kondensationsverbindung
• c) Wasser unter Bildung von Hydraten als Kondensationsverbindung von Aldehyden.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form a chemical bond linking both components. Furthermore, those compounds according to the invention are also included as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to component B is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with

• a) amines and derivatives thereof to form imines or oximes as a condensation compound
• b) alcohols to form acetals or ketals as a condensation compound
• c) water to form hydrates as a condensation compound of aldehydes.

Component A is preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4, 6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethylketal, 4-hydroxy-3-methoxyacetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2- Aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4 '-Trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde , 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxy benzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy 2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy 4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenz aldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6- Dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde hyd, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2- Methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4- methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino 1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro 4-dimethylaminobenzaldehyde, 4-dime thylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylamino-benzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) -benzaldehyde, piperonal, 2,3,6,7- Tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3 aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),
2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3 ', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine , 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromon-3-aldehyde, 3- (5 'Nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde, 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2- Benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) -acetophenone and 2- (3'-pyridoyl) -acetophenone,
Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3 Benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-Benzylidene-cyclohexanone, 2- (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3 -methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) - cyclopentanone, 2- (4'-dimethyl aminobenzylidene) -cyclopentanone,
5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3, 4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl ) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal,
6- (4-Dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5 -dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6 - (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenynhexa-3,5-diene) 2-one,
5- (4-Dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy 3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3 -nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde , 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1 -naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9 -methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolal hyde,
4-Formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1 benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1 methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8- Formyl 1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-Formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6-formyl-1-allylquinolinium, 7-formyl-1 allylchinolini and 8-formyl-1-allyl-quinolinium, 5-acetyl-1-methylquinolinium, 6-acetyl-1-methylquinolinium, 7-acetyl-1-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl 1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-Acetyl-1-benzyl-quinolinium, 8-acetyl-1-benzyl-quinolinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl-1-allyl-quinolinium and 8-acetyl-1 allyl quinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1,3-dimethyl-2- (4'-formylphenyl) -benzimidazolium, 1,3-dimethyl-2 - (4'-formyl-phenyl) -imidazolium, 2- (4'-formyl-phenyl) -3-methyl-benzothiazolium, 2- (4'-acetyl-phenyl) -3-methyl-benzothiazolium, 2- (4'-formyl-phenyl) -3- methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2 '-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3 -methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3 , 5-dimethylbenzothiazolium salts, preferably with benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, Tetrachlorozinkat, methyl sulfate, trifluoromethanesulfonate or tetrafluoroborate as counterion, isatin, 1-methyl-isatin, 1-allyl-isatin , 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures the above connections.

When CH-Acids are generally considered to be compounds which a hydrogen atom bonded to an aliphatic carbon atom carry, due to electron-withdrawing substituents a Activation of the corresponding carbon-hydrogen bond causes becomes. According to the invention, CH-acidic compounds also include enamines. by alkaline treatment of quaternized N-heterocycles with a conjugated to quaternary nitrogen CH-acid Alkyl group arise.

The CH-acidic compounds of component B are preferably selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, Rhodanine, Rhodanine-3-acetic acid, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2-coumaranone, 5-hydroxy-2-coumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1,2-dione, indan-1,3-dione, Indan-1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methylquinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium-p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate.

in der

• – R⁷ für eine Hydroxy- oder eine Aminogruppe, die durch C_1-4Alkyl-, C_1-4Hydroxyalkyl-, C_1-4-Alkoxy- oder C_1-4-Alkoxy-C_1-4-alkylgruppen substituiert sein kann, steht,
• – R⁸, R⁹, R¹⁰, R¹¹ und R¹² unabhängig voneinander für ein Wasserstoffatom, eine Hydroxy- oder eine Aminogruppe, die durch C₁-C₄-Alkyl-, C₁-C₄-Hydroxyalkyl, C₁-C₄-Alkoxy-, C₁-C₄-Aminoalkyl- oder C₁-C₄-Alkoxy-C₁-C₄-alkylgruppen substituiert sein kann, stehen, und
• – P für eine direkte Bindung, eine gesättigte oder ungesättigte, ggf. durch Hydroxygruppen substituierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen-, eine Carbonyl-, Sulfoxy Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine Gruppe mit der Formel III -Q'-(CH₂-Q-CH₂-Q'')_o- (III)in der
• – Q eine direkte Bindung, eine CH₂- oder CHOH-Gruppe bedeutet,
• – Q' und Q'' unabhängig voneinander für ein Sauerstoffatom, eine NR¹³-Gruppe, worin R¹³ ein Wasserstoffatom, eine C_1-4Alkyl- oder eine Hydroxy-C_1-4-alkylgruppe, wobei auch beide Gruppen zusammen mit dem Restmolekül einen 5-, 6- oder 7-Ring bilden können, bedeutet, die Gruppe O-(CH₂)_p-NH oder NH-(CH₂)_p'-O, worin p und p' 2 oder 3 sind, stehen und
• – o eine Zahl von 1 bis 4 bedeutet, wie beispielsweise 4,4'-Diaminostilben und dessen Hydrochlorid, 4,4'-Diaminostilben-2,2'-disulfonsäure-mono- oder -di-Na-Salz, 4-Amino-4'-dimethylaminostilben und dessen Hydrochlorid, 4,4'-Diaminodiphenylmethan, 4,4'-Diaminodiphenylsulfid, 4,4'-Diaminodiphenylsulfoxid, 4,4'-Diaminodiphenylamin, 4,4'-Diaminodiphenylamin-2-sulfonsäure, 4,4'-Diaminobenzophenon, 4,4'-Diaminodiphenylether, 3,3',4,4'-Tetraaminodiphenyl, 3,3',4,4'-Tetraamino-benzophenon, 1,3-Bis-(2,4-diaminophenoxy)-propan, 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctan, 1,3-Bis-(4-aminophenylamino)propan, 1,3-Bis-(4-aminophenylamino)propan, 1,3-Bis-[N(4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-Bis-[2-(4-aminophenoxy)-ethyl]-methylamin, N-Phenyl-1,4-phenylendiamin und Bis-(5-amino-2-hydroxyphenyl)-methan.

Preferred primary or secondary aromatic amines of component B are selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2.5- Dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-methylphenol, 2- 2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4- Methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) -phen ol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 2- (diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) -benzene, 1-hydroxy-2-amino-5-methylbenzene, 1-hydroxy-2-amino 6-methylbenzene, 2-amino-5-acetamidophenol, 1,3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) -2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2 -hydroxyethoxy) -toluene, 2,4-diamino-5-methylphenol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) -anisole, 2,6-bis- (2-hydroxyethylamino) -1-methylbenzene, 1,3-diamino-2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzene benzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-aminobenzene sulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene 2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrcatechol, 4,6-diaminopyrogallol, 1- (2-hydroxybenzoyl) 5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2-hydroxyphenynemethyl) piperazinyl) methyl] phenol, 3,5-diamino-4-hydroxy-catechol, 1,4-bis - (4-aminophenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro group-containing amino compounds such as 3 -Amino-6-methylamino-2-nitro-pyridine, pikramic acid, [8 - [(4-amino-2 -nitrophenyl) -azo] -7-hydroxy-naphth-2-yl] -trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) azo) -7-hydroxy-naphth-2-yl] -trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [bis (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2 -hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1-amino-2-nitro-4 - [(2-hydroxyethyl) amino] -benzene (HC Red No. 7), 2-chloro-5 -nitro-N-2-hydroxyethyl-1,4-phenylenediamine, 1 - [(2-hydroxyethynamino) -2-nitro-4-aminobenzene (HC Red # 3), 4-amino-3-nitrophenol, 4 -Amino-2-nitrophenol, 6-nitro-o-toluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 1-amino-2 -nitro-4 - [(2,3-dihydroxypropyl) amino] -5-chlorobenzene (HC Red No. 10), 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro-2,5 -diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid blue No. 29), 1 amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid Disodium salt (palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (gallium), 4-amino-4'-nitrostilbene-2 , 2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methylazobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2- (diethylamino) ethylamino] -5-nitroaniline, 3-amino 4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, Anilines, in particular nitro-group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4 Nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1-amino-4- [bis (2-hydroxyethyl) amino] benzene , 4-Amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethyl lamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in formula II

in the

• R ^{7 represents} a hydroxy or an amino group which may be substituted by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy or C _1-4 alkoxy C _1-4 alkyl groups can, stands,
• R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently of one another represent a hydrogen atom, a hydroxy or an amino group which is represented by C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₄ aminoalkyl or C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl groups may be substituted, and
• - P for a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy sulfonyl or imino group, an oxygen or sulfur atom, or a group of formula III -Q '- (CH ₂ -Q-CH ₂ -Q'') _o - (III) in the
• Q is a direct bond, a CH ₂ or CHOH group,
• - Q 'and Q''independently represent an oxygen atom, an NR ¹³ group, wherein R ¹³ is a hydrogen atom alkyl group, a C _1-4 alkyl or a hydroxy-C _1-4 wherein both groups together with the Residual molecule can form a 5-, 6- or 7-membered ring, the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _{p '} -O, wherein p and p' are 2 or 3, stand and
• O is a number from 1 to 4, such as, for example, 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino 4'-dimethylaminostilbene and its hydrochloride, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylamine, 4,4'-dia minodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraaminobenzophenone, 1,3- Bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, 1,3-bis - (4-aminophenylamino) propane, 1,3-bis [N (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- (4-aminophenoxy) ethyl] methylamine , N-phenyl-1,4-phenylenediamine and bis (5-amino-2-hydroxyphenyl) -methane.

The the aforementioned compounds both in free form and in the form of their physiologically acceptable Salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid, can be used.

Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-aminopyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3, 5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4-dimethyl-pyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-) 2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4.5, 6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1,2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino 2,3-dimethyl-1-p henyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinaldine, 2-aminonicotinic acid, 6-aminonicotinic acid , 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino-aniline and indole and indoline derivatives, such as 4-aminoindole , 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Furthermore, as heterocyclic compounds according to the invention in the DE-U1-299 08 573 disclosed hydroxypyrimidines can be used. The aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.

suitable aromatic hydroxy compounds are, for. 2-methylresorcinol, 4-methylresorcinol, 5-methyl, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, Hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxy-phenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

The Compounds of component A and the compounds of the component B are preferably used in the compositions in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the entire shading agent used. The molar ratio of the compound of component A and the compound of the component B may range from 0.5 to 2.0, preferably equimolar amounts be used. The actual Nuanciermittel is at separate Storage of components A and B immediately before use Mixing produced.

When Precursors of naturally-analogous dyes are preferred as the oxidation dye precursor Of the developer type such indoles and indolines used, at least a 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 a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

in der unabhängig voneinander

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

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

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,

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

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

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

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,
• - 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.

Preferred substantive dyes used in the compositions as color-modifying components are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations 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-nitrobenzene 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) aromatischere 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 Heterozyklus 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.

Further, the agents may 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) more 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 described for example in the EP-A2-998 908 to which reference is made at this point, are called in the claims 6 to 11.

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

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive Dyes of group (c).

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

The Agents contain the direct dyes preferably in one Amount of 0.01 to 20 wt .-%, based on the ready-to-use Medium.

Farther can the preparations also occurring in nature dyes such 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 it is not necessary that the oxidation dye precursors or the direct dyes in each case uniform compounds represent. Rather, you can in the compositions due to the manufacturing processes for the individual dyes, in minor amounts contain other components be, as far as this is not the dyeing result adversely affect or for other reasons, e.g. toxicological, must be excluded.

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.

• – mindestens eine Entwicklerkomponente und gegebenenfalls mindestens eine Kupplerkomponente und/oder
• – mindestens einen direktziehenden Farbstoff

bedeutet, die zweite Komponente eine Oxidationsmittelzusammensetzung, enthaltend mindestens ein chemisches Oxidationsmittel, insbesondere Wasserstoffperoxid, ist und mindestens eine der beiden Komponenten mindestens eine Verbindung gemäß Formel (I) enthält,

worin
R¹, R² und R³ unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₄-Hydroxyalkylgruppe stehen,
R⁴ ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₅-Acylgruppe bedeutet,
R⁵ für ein Wasserstoffatom, eine negative Ladung oder eine C₁- bis C₄-Alkylgruppe steht.Another embodiment of the composition is a hair dye which is mixed immediately prior to use of two components, wherein the first component comprises an agent contained in a carrier

• At least one developer component and optionally at least one coupler component and / or
• - At least one direct dye

the second component is an oxidizing agent composition containing at least one chemical oxidizing agent, in particular hydrogen peroxide, and at least one of the two components contains at least one compound according to formula (I),

wherein
R ¹ , R ² and R ³ independently of one another represent a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group,
R ⁴ denotes a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₅ -acyl group,
R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group.

Prefers contains in this embodiment the first component at least one compound of the formula (I).

Also for this embodiment All embodiments apply the compound of the formula (I) according to the first subject of the invention.

In general, an oxidative dyeing can be carried out in the presence of atmospheric oxygen in the presence of oxidation dye precursors. Preferably, however, a chemical oxidizing agent (also called oxidizing agent) is used, especially if, in addition to the coloring, a whitening effect of the natural pigments of the human hair is desired. This lightening effect may be desired regardless of the staining method. Accordingly, the presence of oxidation dye precursors is not a mandatory requirement for the use of oxidizing agents in the cosmetic compositions of the process according to the invention. The chemical oxidizing agent is in particular hydrogen peroxide and / or at least one addition product thereof, in particular inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone · H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide in question. The actual colorant is prepared by separate storage of the dye precursors and the chemical oxidant immediately before use by mixing. In a preferred embodiment, therefore, the agent before application of a composition comprising in a cosmetic carrier at least one color-changing component, and a further composition comprising in a cosmetic Carrier at least one oxidizing agent, mixed.

The actual (oxidative) hair dye is expediently just prior to application by mixing a separate oxidizer composition with the color-changing ones Components contained composition, preferably in the weight ratio range from 1 to 4 to 4 to 1, in particular from 1 to 2 to 2 to 1, prepared.

According to the invention that dye 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. The catalysts can also be used in the presence of a Oxidizing agent can be used.

Suitable metal ions are, for example, Zn ^{2 +,} Cu ^{2 +,} Fe ^{e +,} 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.

at an application of oxidants becomes the ready to use Preparation expediently immediately before use by mixing a composition, containing the oxidizing agent with the composition containing the color-changing ones Components, manufactured. The resulting ready-to-use Hair dye preparation should preferably have a pH in the range of 6 to 12. Especially Preferably, the use of the colorants in a weak alkaline environment.

worin
R¹, R² und R³ unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₄-Hydroxyalkylgruppe stehen,
R⁴ ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₆-Acylgruppe bedeutet,
R⁵ für ein Wasserstoffatom, eine negative Ladung oder eine C₁- bis C₄-Alkylgruppe steht.Another embodiment of the composition is a hair bleach which is mixed immediately prior to use of two components, wherein the first component comprises an agent containing in a carrier at least one alkalizing agent and optionally at least one bleach booster, the second component an oxidizing agent composition containing at least one chemical Oxidizing agent, in particular hydrogen peroxide, and at least one of the two components contains at least one compound according to formula (I),

wherein
R ¹ , R ² and R ³ independently of one another represent a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group,
R ⁴ denotes a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₆ -acyl group,
R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group.

For a color change by brightening or equation of the hair are preferred next the chemical oxidizing agents additionally used at least one bleach booster.

Be bleach preferably in Blondiermitteln to increase the Blondierwirkung the chemical oxidizing agent, in particular the hydrogen peroxide, used.

When bleach booster can Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

Bleaching amplifiers are preferably peroxo compounds. Among the bleaching according to the invention Peroxo compounds are not subject to the addition of hydrogen peroxide to other components and not even hydrogen peroxide itself. The choice of peroxo compounds is also subject no restrictions. Preferred peroxo compounds are peroxydisulfate salts, monopersulfate salts, (in particular ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, Ammonium monopersulfate, potassium monopersulfate, sodium monopersulfate, Potassium peroxide phosphate) and peroxides (such as barium peroxide, calcium peroxide and magnesium peroxide). Among these peroxo compounds, too can be used in combination, according to the invention are the inorganic Compounds preferred. Particularly preferred are the peroxydisulfates, in particular ammonium peroxydisulfate.

The bleach booster are preferred in amounts in the ready-to-use compositions from 5-30 Wt .-%, in particular in amounts of 8-20 wt .-%, included.

The cosmetic compositions, when acting as bleaching agents, contain as preferred alkalizing agent at least one compound selected from ammonia, ammonium, alkali metal and alkaline earth metal hydroxides,
carbonates, bicarbonates, hydroxycarbonates, metasilicates and carbamides, as well as alkali phosphates and alkanolamines such as 2-ethanolamine.

The Ready-to-use agent can in the embodiment as dyeing or Bleaching a non-physiological Have pH. It should preferably have a pH in the range of pH 7.5 to pH 12, in particular from pH 7.5 to pH 11.

The Means can additionally all known in this field and commonly used Wirk- and Excipients included.

In many cases contain the funds additionally 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),
• – anionische Alkyloligoglykoside bzw. anionische Alkenyloligoglykosid-Derivate, ausgewählt aus Alkyl- und/oder Alkenyl-Oligoglykosidcarboxylaten, -sulfaten, -phosphaten und/oder -isethionaten, die sich von Alkyl- und/oder Alkenyloligoglykosiden der allgemeinen Formel (V) ableiten,

R-O-(G)_p (V)mit der Bedeutung
R C_6-22-Alkyl oder C_6-22-Alkenyl,
G Glykosideinheit, die sich von einem Zucker mit 5 oder 6 Kohlenstoffatomen ableitet,
p Zahl von 1 bis 10,
insbesondere das Laurylglucosidcarboxylat, wie es als Plantapon^® LGC von Cognis Deutschland erhältlich ist.

• – 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 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),
• Anionic alkyl oligoglycosides or anionic alkenyl oligoglycoside derivatives selected from alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates derived from alkyl and / or alkenyl oligoglycosides of general formula (V),

RO- (G) _p (V) with the meaning
RC _6-22 alkyl or C _6-22 alkenyl,
G glycoside unit, which is derived from a sugar with 5 or 6 carbon atoms,
p number from 1 to 10,
in particular the Laurylglucosidcarboxylat as it is available as Plantapon ^® LGC from Cognis Germany.

• 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 Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether 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,
• – C₁₂-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 ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with 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 C₁₂- und C₁₄-Alkylgruppen,
• – im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen besteht.

Particular preference is given to those alkylpolyglycosides in which R ¹

• Consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• Essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Essentially from C ₈ - to C ₁₆ alkyl groups or
• - Consists essentially of C ₁₂ - to C ₁₆ -alkyl groups.

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 resort to the preparations.

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 cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. 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 understood as meaning those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each 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 as cationic surfactants, especially those of the quaternary ammonium type, the esterquats and amidoamines used.

preferred quaternary Ammonium compounds are ammonium halides, especially chlorides and Bromides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants are preferred 10 to 18 carbon atoms.

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 trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, and Dehy quart ^® 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 under the name Tegoamid ^® S 18 commercial 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 commercially available product Glucquat ^® 100 is, 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 - alcoholates be used as catalysts. The use of products with narrow homolog distribution may be preferred.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte 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/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – 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 agents can other 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-dimethyldiallyl-ammonium 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, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• - 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, included.

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 Contains funds the ingredients of the invention in a cosmetic carrier. Such carriers are For example, creams, emulsions, gels or surfactant-containing foaming Solutions, such as shampoos, foam aerosols or other preparations, especially for the application on the hair are suitable. But it is also conceivable the ingredients in a powdered or tablet-like formulation which is dissolved in water before use. The carriers can especially watery or be watery-alcoholic.

One aqueous carrier contains at least 50% by weight of water.

For the purposes of the present invention, aqueous-alcoholic carriers are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alcohol, in particular ethanol or isopropanol. 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.

One Fourth object of the present invention is a cosmetic Method of hair treatment in which a means according to the third Subject of the invention on hair and the hair roots bearing skin is applied and rinsed again after an exposure time.

The Application temperatures can in a range between 15 and 40 ° C. After an exposure time of usually 5 to 45 minutes, the agent is made by rinsing off Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, e.g. a shampoo was used.

• (A) in einem ersten Schritt Haar und dessen Haarwurzeln tragende Hautpartien mit einem ersten Haarbehandlungsmittel behandelt wird und
• (B) in einem zweiten Schritt im Anschluß an den ersten Schritt, das heißt im Abstand von bis zu 12 Stunden, bevorzugt direkt im Anschluß daran, auf das im ersten Schritt behandelte Haar und dessen Haarwurzeln tragende Hautpartien ein zweites Haarbehandlungsmittel aufgetragen wird, welches mindestens eine Verbindung gemäß Formel (I) enthält,

worin
R¹, R² und R³ unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₄-Hydroxyalkylgruppe stehen,
R⁴ ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₆-Acylgruppe bedeutet,
R⁵ für ein Wasserstoffatom, eine negative Ladung oder eine C₁- bis C₄-Alkylgruppe steht.
und nach einer Einwirkungszeit wieder abgespült wird.A fifth item is a cosmetic procedure in which

• (A) in a first step hair and the hair roots bearing skin is treated with a first hair treatment agent and
• (B) in a second step following the first step, ie at intervals of up to 12 hours, preferably directly following, a second hair treatment composition containing at least one compound according to formula (I) is applied to the skin areas which are treated in the first step and the hair roots bearing hair roots,

wherein
R ¹ , R ² and R ³ independently of one another represent a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group,
R ⁴ denotes a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₆ -acyl group,
R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group.
and rinsed again after a contact time.

A "treatment" according to the first Step is preferred according to the invention by application of a corresponding cosmetic composition. After expiration of a contact time, the cosmetic composition rinsed out again.

When Hair treatment compositions of the first step find especially hair dyes or hair bleach use in a cosmetic vehicle at least a chemical oxidant and / or at least one color-modifying agent Component included.

The Application temperatures for both steps can in a range between 15 and 40 ° C. After an exposure time of usually 5 to 45 minutes, the agent is made by rinsing off Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, e.g. a shampoo was used.

The Provision of multi-component cosmetic compositions containing in the inventive method Can be used takes place in a packaging unit (kit) containing the corresponding components contains or merges.

The Means can therefore be in a packaging unit (kit), which at least a separately prepared, inventive means of the fifth subject of the invention contains to be provided. additionally For example, the kit may contain at least one separately formulated oxidizer composition contain, especially if an (oxidative) colorant should be provided.

• – in einem Container C1 eine kosmetische Zusammensetzung, die in einem kosmetischen Träger mindestens eine Verbindung der Formel (I) enthält,
  
  worin R¹, R² und R³ unabhängig voneinander für eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₄-Hydroxyalkylgruppe stehen, R⁴ ein Wasserstoffatom, eine C₁- bis C₄-Alkylgruppe oder eine C₂- bis C₆-Acylgruppe bedeutet, R⁵ für ein Wasserstoffatom, eine negative Ladung oder eine C₁- bis C₄-Alkylgruppe steht,
• – in einem Container C2 eine kosmetische Zusammensetzung, die in einem kosmetischen Träger mindestens einen kosmetischen Wirkstoff enthält.

A sixth aspect of the invention is a kit containing

• In a container C1, a cosmetic composition containing, in a cosmetic carrier, at least one compound of the formula (I),
  
  wherein R ¹ , R ² and R ³ independently of one another are a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group, R ^{4 is} a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ to C ₆ acyl group, R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group,
• In a container C2, a cosmetic composition containing in a cosmetic carrier at least one cosmetic active substance.

The cosmetic active ingredient is preferably selected from chemical oxidizing agents and / or color-changing components. Preferred representatives of these ingredients according to the invention were defined for the second or third subject of the invention.

• (a) aus mindestens einem Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens einer Kupplerkomponente und/oder
• (b) aus Oxofarbstoffvorprodukten und/oder
• (c) aus mindestens einem direktziehenden Farbstoff und/oder
• (d) aus mindestens einer Vorstufe naturanaloger Farbstoffe.

It is inventively preferred if the composition of the container C2 contains as additional, cosmetic active ingredient at least one chemical oxidizing agent. In this case, it is again preferred if the cosmetic agent of the container C1 additionally contains at least one color-changing component which is selected,

• (A) from at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or
• (b) from oxo dye precursors and / or
• (c) from at least one direct dye and / or
• (D) from at least one precursor of natural dyes.

suitable Representatives of the categories have already been defined within the scope of the fifth subject of the invention.

Furthermore The kit may be additional optional instructions for use, application aids, mixing vessels or Protective gloves included.

The Compositions of the kit can be mixed before the application, or successively on the hair come into use.

Examples

All amounts are, unless otherwise stated wt .-%, each based on the weight of the respective recipe. 1. hair dye cetyl alcohol 18,00 Ammonium polyacrylate 0.12 potassium oleate 13,00 Ammonia (25% aqueous solution) 12,00 Oleth-7 4.00 Ammonium acrylate copolymer 5.00 L_Acetylcarnitin 3.00 oleate 2.00 glyceryl stearate 3.00 Kaliumcastorat 2.00 Linoleamidopropyl PG-Dimonium Chloride Phosphate 1.00 Titanium dioxide 0.50 decyl glucoside 0.50 Perfume 0.50 silica 0.25 p-toluenediamine 0.14 4-chlororesorcinol 0.04 2-methyl 0.03 2-amino-3-hydroxypyridine 0.01 Tetrasodium EDTA 0.50 Polyquaternium-2 0.30 sodium 0.10 potassium hydroxide 0.10 ascorbic acid 0.50 water ad 100

The The above recipe was made according to known manufacturing method provided. Before the application was above recipe with a aqueous 6 wt .-% hydrogen peroxide lotion in a weight ratio of 1 mixed to 1 and the mixture applied to the hair and after rinsed out for a period of 30 minutes.

It was also carried out by the same process, a coloration with mixing of the above formulation with an aqueous 9 wt .-% hydrogen peroxide lotion. 2. hair dye cetyl alcohol 18,00 Ammonium polyacrylate 0.12 potassium oleate 13,00 Ammonia (25% aqueous solution) 12,00 Oleth-7 4.00 Ammonium acrylate copolymer 5.00 L-carnitine tartrate 4.00 oleate 2.00 glyceryl stearate 3.00 Kaliumcastorat 2.00 Linoleamidopropyl PG-Dimonium Chloride Phosphate 1.00 Titanium dioxide 0.50 decyl glucoside 0.50 Perfume 0.50 silica 0.25 p-toluenediamine 0.14 4-chlororesorcinol 0.04 2-methyl 0.03 2-amino-3-hydroxypyridine 0.01 Tetrasodium EDTA 0.50 Polyquaternium-2 0.30 sodium 0.10 potassium hydroxide 0.10 ascorbic acid 0.50 water ad 100

The above recipe was provided according to a known manufacturing method. Before use, the above formulation was mixed with an aqueous 3 wt .-% hydrogen peroxide lotion in a weight ratio of 1 to 1 and the mixture applied to the hair and rinsed out again after a contact time of 30 minutes. 3. hair tonic cetyl alcohol 2.00 Ammonium polyacrylate 0.25 Sodium Laureth Sulphate 3.30 3-methoxybutanol 5.00 cetearyl 1.50 myristyl 2.00 L-carnitine tartrate 2.00 Polyquaternium-6 0.30 Ceteareth-20 1.00 propylene glycol 3.00 4-hydroxypropylamino-3-nitrophenol 2.50 Natriumpikramat 1.00 4-amino-3-nitrophenol 1.50 water ad 100

4. Proof of apoptosis protection

In this colorimetric study it was examined to what extent hair follicles differ, which were treated either with a placebo formulation (application mixture prepared according to example 2 without carnitine tartrate) or with an oxidative coloring with carnitine tartrate additive (application mixture prepared according to example 2). For this purpose, in the half-page test 21 subjects were on a half page with the placebo formulation over a period of 30 minutes and on the other half page with the formulation according to Example 2 treated.

15h After application, each test subject had hair follicles on each half side plucked to obtain RNA. With the help of RNA were different apoptosis-relevant markers (Bax, Bcl-2, caspase 2, caspase 3, caspase 9, TNFalpha and cyclooxygenase 2) by polymerase chain reaction (PCR). The PCR gives information the genetic information stored in the cell, i. the genes, which are activated or deactivated by the treatment. The investigations show that by the addition of carnitine tartrate apoptosis in the treated hair follicles can be significantly reduced.

4.1 The ratio Bax / Bcl-2

For the evaluation, the quotient of the respective gene expression was formed and the two quotients (placebo / example 2) were compared. The ratio of Bax and Bcl-2 is important because the pro-apoptotic (bax) and anti-apoptotic (Bcl-2) markers usually balance each other. If the equilibrium is influenced in favor of a marker, this can be said about apoptosis. If, for example, the ratio Bax / Bcl-2 decreases due to an increase in Bcl-2, this indicates increased apoptosis protection. To study gene expression, the total of 21 subjects were divided into 5 pools to reduce the number of samples. Table 1: pool Example 2 without carnitine tartrate Example 2 (according to the invention) Ratio Bax / Bcl-2 Ratio Bax / Bcl-2 1 3.41 2.88 2 4.34 3.7 3 10.05 6.03 4 7.36 5.15 5 5.05 3.52 Average 6.04 4.25

By the formulation with carnitine tartrate of Example 2 could relationship between Bax and Bcl-2 15 hours after coloration. The quotient of Bax and Bcl-2 is in all pools with carnitine tartrate lower than the formulation without carnitine tartrate. That the Apoptosis was in terms of increased apoptosis in the Hair follicle cells decreased.

4.2 Caspases, TNFalpha, Cox2

to facilitated overview the values of control treated with placebo formulation were found set the value 1 and the change expression in the follicles treated with the agent according to Example 2 as an x-fold change shown)

4.2.1 Caspases

Table 2: pool Caspase 2 Caspase 3 Caspase 9 1 -1.7 -2.8 -1.5 2 -1.3 1.1 1.1 3 -1.6 -1.3 -1.7 4 -1.3 -1.3 1.2 5 -1.5 -1.3 -1.2

The studies show that in almost all pools the expression of apoptotic markers, though to varying degrees, can be reduced by the addition of carnitine tartrate in the coloration formulation.

4.2.2 TNFalpha, Cox2

Table 3: pool TNFaplha Cox2 1 -1.1 -1.9 2 -2.8 -1.6 3 -1.3 -1.9 4 -1.9 -1.1 5 -3.0 -1.1

The Investigations show that in all pools the expression of the apoptosis markers, though to varying degrees, by the addition of carnitine tartrate can be reduced in the coloration formulation.

Claims (14)

Cosmetic use of at least one compound according to formula (I)

wherein R ¹ , R ² and R ³ independently of one another are a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group, R ^{4 is} a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₆ acyl group, R ^{5 is} a hydrogen atom, a negative charge or a C ₁ - to C ₄ alkyl group, to protect the hair, especially the hair follicle cell, from stress factors. Use according to claim 1, characterized that this favored by stressors, premature Death of the hair, especially the hair follicle cell prevented or diminished. Use according to one of claims 1 or 2, characterized that the favored by stressors, premature failure of the hair is prevented or diminished. Use of at least one compound according to formula (I)

wherein R ¹ , R ² and R ³ independently of one another are a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group, R ^{4 is} a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ to C ₆ acyl group, R ^{5 is} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group, for the preparation of an agent for protecting the hair, in particular the hair follicle cells, from stress factors. Use of at least one compound according to formula (I)

wherein R ¹ , R ² and R ³ independently of one another are a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group, R ^{4 is} a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ to C ₆ acyl group, R ^{5 represents} a hydrogen atom, a negative charge or a C ₁ to C ₄ alkyl group, for the preparation of an agent for the protection against stress factors caused by premature hair loss. Use according to one of claims 1 to 5, characterized in that in formula (I) the radicals R ¹ , R ² and R ³ independently of one another represent a methyl or an ethyl group. Use according to one of claims 1 to 5, characterized that the Compound according to formula (I) from at least one compound of the group L-carnitine, D-carnitine, D, L-carnitine, L-carnitine tartrate, D-carnitine tartrate, D, L-carnitine tartrate, L-carnitine lactate, D-carnitine lactate, D, L-carnitine lactate, L-carnitine citrate, D-carnitine citrate, D, L-carnitine citrate, L-acetylcarnitine, D-acetylcarnitine and D, L-acetylcarnitine is chosen. Use according to one of Claims 4 to 7, characterized that this Additional funds at least one color-changing Component contains. Use according to claim 8, characterized that the color-changing Component selected becomes (a) from at least one oxidation dye precursor of the type of developer components and, if appropriate, at least in addition a coupler component and / or (b) from oxo dye precursors and or (c) from at least one direct dye and or (D) from at least one precursor of natural dyes and or (e) at least one oxidizing agent and optionally additionally at least one bleach booster. Use according to one of claims 8 or 9, characterized that this Additional means at least contains a chemical oxidant. Use according to one of claims 4 to 10, characterized that this Additional means at least contains a surfactant. Cosmetic process for hair treatment, in which a means according to one the claims 4 to 11 applied to hair and hair roots bearing skin is rinsed off and after a contact time again. Cosmetic process, in which (A) in a first step hair and hair roots bearing skin parts with a first hair treatment agent containing at least one chemical oxidant and / or at least one color-changing component and (B) in a second step following the first step, that is, at intervals of up to 12 hours, preferably directly after, a second hair treatment composition containing at least one compound according to formula (I) is applied to the skin parts bearing hair treated in the first step and the hair roots thereof,

wherein R ¹ , R ² and R ³ independently of one another are a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₄ -hydroxyalkyl group, R ^{4 is} a hydrogen atom, a C ₁ - to C ₄ -alkyl group or a C ₂ - to C ₆ acyl group, R ^{5 stands} for a hydrogen atom, a negative charge or a C ₁ - to C ₄ alkyl group. and rinsed again after a contact time. Kit comprising - in a container C1, a cosmetic composition containing in a cosmetic carrier at least one compound of the formula (I),

wherein R ¹ , R ² and R ^{3 are} independently a C ₁ to C ₄ alkyl group or a C _{2 to} C ₄ hydroxyalkyl group, R ^{4 is} a hydrogen atom, a C ₁ to C ₄ alkyl group or a C ₂ -to C ₆ -acyl group, R ^{5 is} a hydrogen atom, a negative charge or a C ₁ - to C ₄ -alkyl group, - in a container C2, a cosmetic composition which contains at least one chemical oxidizing agent in a cosmetic carrier and / / or at least one color-modifying component.