DE10129466A1 - Composition for dyeing keratinic fibers, especially human hair, comprises conjugate of care product and dye - Google Patents

Abstract

Composition for dyeing keratinic fibers comprises a conjugate (I) of a care product and a dye. Composition for dyeing keratinic fibers comprises a conjugate of formula (I): (I) P-(S-F)x x = 1-3; P = a care component; F = a dye component; and S = a direct bond, a spacer group or a common structural element of P and F. An Independent claim is also included for use of the above composition for dyeing human skin.

Description

The invention relates to new caring hybrid dyes and caring Dyestuffs containing hybrid dye precursors, which are particularly suitable for dyeing keratin fibers are the nourishing hybrid dyes contained in these agents and nourishing Hybrid dye precursors, the use of these colorants and those contained in them nourishing hybrid dyes and hybrid dye precursors.

Human hair today is used in many different ways with hair cosmetic preparations treated. This includes, for example, cleaning the hair with shampoos and care and regeneration with rinses and treatments as well as bleaching, dyeing and shaping of the hair with colorants, tinting agents, waving agents and styling preparations. there play a role in changing or shading the color of the scalp hair prominent role. You can see from the bleaching agents that have an oxidative brightening the hair by breaking down the natural hair dyes, are in the area Hair dyeing has three main types of hair dye:

For permanent, intensive dyeings with appropriate fastness properties so-called oxidation coloring agents are used. Such colorants usually contain Oxidation dye precursors, so-called developer components and Intermediates. The developer components form under the influence of oxidizing agents or of atmospheric oxygen among themselves or under coupling with one or more Coupler components from the actual dyes. The oxidation colorants stand out by excellent, long-lasting dyeing results. For natural looking ones However, dyeings usually have to be a mixture of a large number of Oxidation dye precursors are used.

In many cases, direct dyes are still used for shading. Assign the dyes formed or directly used in the course of color formation significantly different fastness properties (e.g. UV stability, perspiration fastness, wash fastness etc.), it can become recognizable and therefore undesirable over time Color shift come. This phenomenon occurs more when the hairstyle or hair Hair zones have different degrees of damage. Long examples are an example Hair with hair tips exposed to all environmental influences for a long time As a rule, they are significantly more damaged than the relatively freshly regrown hair zones.

For temporary coloring, colorants or tints are usually used contain so-called direct draw as a coloring component. This is Dye molecules that pull directly onto the hair and do not have an oxidative process Need more color training. These dyes include, for example Henna known from antiquity for coloring body and hair. This Colorings are usually much more sensitive to shampooing than that oxidative dyeings, so that a much undesirable then much faster Shift in nuance or even a visible "discoloration" occurs.

Furthermore, a novel dyeing process has received great attention recently. In this process, precursors of the natural hair dye melanin, in particular derivatives of indole or indoline, applied to the hair and form in the frame oxidative processes in hair practically nature-identical dyes. Such one Process with 5,6-dihydroxyindolines as dye precursors was described in EP-B1-530 229 described. With, in particular multiple, use of funds with 5,6-dihydroxyindoline it is possible for people with gray hair the natural hair color play. Coloring can take place with atmospheric oxygen as the only oxidizing agent, so that no further oxidizing agents have to be used.

A further alternative are coloring systems based on isatin or isatin derivatives. Isatin is a direct dye for dyeing keratin fibers alone or in combination with Quinone dyes described in German Offenlegungsschrift DE-A 36 35 147 Service. However, the range of variations of the nuances that can be achieved is limited. In the in most cases you get a golden color. Also as Oxidation dye precursors are already known as isetate derivatives. In the German Laid-open specification DE-A 27 16 671 are diaminoisatins as coupler substances described in the presence of a developer and an oxidizing agent brown to black colors result.

A completely different dyeing process for keratin fibers is described in EP-A 359 465 described. Here the coloring is done with the help of a reaction from an isatin derivative achieved with an aniline derivative of ketimine. The ketimine is either considered such applied to keratin fibers and develops a color there, or else a mixture consisting of an isatin derivative and an aniline derivative is applied to the The fiber is applied and initially forms the ketimine "in situ", whereupon it forms on the fiber the coloring developed. The coloring is in both cases without the addition of Oxidizing agents achieved.

Commercial hair dye products usually contain a mixture of about 3 to 8 different dyes and / or dye precursors. The individual dyes but usually have different absorption, light, welding, friction and Wash fastnesses, which also strongly depend on the structural properties and the Grooming condition of the hair can be dependent. Above all, these differences are pronounced if, as for many nuances so far indispensable, direct dyes used to adjust the shade in oxidation colorants.

It is therefore often more extensive when developing new hair dyes Try not only to achieve certain nuances, but above all to ensure that the coloring over the desired period in both the shade and in the Intensity is stable.

There is also a great need for hair dyes that are not only at the same time coloring, but also nourishing properties, so an excessive Stress on the hair with frequent dyeing is avoided and an even one Coloring result is achieved due to an evenly healthy structure of the hair.

There is also a great need for hair dyes, especially temporary ones Hair dye, which in addition to the properties mentioned above, also a good one Have wash resistance.

It has now surprisingly been found that many of the above problems can be completely or at least partially avoided if colorants are used that contain substances that have both nourishing and coloring components unite in itself. In particular, it has been shown that such substances and such Substances containing substances over a very good, with known hair dyes or Hair dye precursors have at least comparable absorbency to the hair feature and lead to brilliant, intensive hair coloring. Because of the molecular Linking with the care component P, the problem can be different Fastness properties of the dyes or dye precursors in many cases largely overcome. In addition, the molecular link becomes a even distribution of both the care components and the Dye components guaranteed on the hair.

Furthermore, these substances as well as coloring agents containing these substances at the same time, excellent nourishing properties. So these substances or Significant structure-stabilizing effects. Furthermore, these continue to excel characterized by high washing stability.

The present invention therefore firstly relates to agents for dyeing keratin fibers which contain at least one nourishing hybrid dye and / or at least one nourishing hybrid dye precursor of structure (I),

P - (S - F) _x (I)

in which x is an integer from 1 to 3; and
P stands for a care component,
F stands for a dye component; and
S stands for a structural element that is a common component of groups P and F, a direct bond or at least one spacer group.

The caring hybrid dyes and / or hybrid dye precursors according to the invention Containing colorants are ideal for dyeing keratin fibers. Keratinic fibers include furs, wool, feathers and in particular human Understand hair. In principle, however, the colorants according to the invention can also be used for Dyeing other natural fibers such. B. cotton, jute, sisal, linen or silk, modified natural fibers, such as. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as. B. polyamide, polyacrylonitrile, Polyurethane and polyester fibers are used. One use on another Areas, especially in color photography, are therefore not in conflict.

As already explained above, the structural principles form well-known care substances and Dye classes form the basis for the newly developed nourishing hybrid dyes and / or Hybrid dye precursors.

Group P is derived from hair care components. As part of the present Invention hair care components are understood to mean those substances that have a have a demonstrably positive effect on the hair structure, e.g. B. the so-called "cortical modifiers".

• - linearen und/oder verzweigten Fettsäuren, bevorzugt C₂-C₃₀-Fettsäuren, besonders bevorzugt C₄-C₁₈-Fettsäuren, am meisten bevorzugt C₆-C₁₀-Fettsäuren und/oder deren physiologisch verträglichen Salzen; Weitere Beispiele leiten sich ab von den Carbonsäuren wie Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Isobuttersäure, Valeriansäure, Isovaleriansäure, Pivalinsäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Milchsäure, Glycerinsäure, Glyoxylsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Propiolsäure, Crotonsäure, Isocrotonsäure, Elaidinsäure, Maleinsäure, Fumarsäure, Muconsäure, Citraconsäure, Mesaconsäure, Camphersäure, Benzoesäure, o,m,p-Phthalsäure, Naphthoesäure, Toluoylsäure, Hydratropasäure, Atropasäure, Zimtsäure, Isonicotinsäure, Nicotinsäure, Bicarbaminsäure, 4,4'-Dicyano-6,6'-binicotinsäure, 8-Carbamoyloctansäure, 1,2,4- Pentantricarbonsäure, 2-Pyrrolcarbonsäure, 1,2,4,6,7-Napthalinpentaessigsäure, Malonaldehydsäure, 4-Hydroxy-phthalamidsäure, 1-Pyrazolcarbonsäure, Gallussäure oder Propantricarbonsäure, sowie von den Dicarbonsäuren ausgewählt aus der Gruppe, die gebildet wird durch Verbindungen der allgemeinen Formel (II),
  
  
  in der Z steht für eine lineare oder verzweigte Alkyl- oder Alkenylgruppe mit 4 bis 12 Kohlenstoffatomen, n für eine Zahl von 4 bis 12 sowie eine der beiden Gruppen X und Y für eine COOH-Gruppe und die andere für Wasserstoff oder einen Methyl- oder Ethylrest, Dicarbonsäuren der allgemeinen Formel (II), die zusätzlich noch 1 bis 3 Methyl- oder Ethylsubstituenten am Cyclohexenring tragen sowie Dicarbonsäuren, die aus den Dicarbonsäuren gemäß Formel (II) formal durch Anlagerung eines Moleküls Wasser an die Doppelbindung im Cyclohexenring entstehen;
• - linearen und/oder verzweigten und gesättigten und/oder ungesättigten Alkoholen, bevorzugt C₂-C₃₀-Alkoholen, besonders bevorzugt C₄-C₂₄-Alkoholen, am meisten bevorzugt C₆-C₂₂-Alkoholen; wie beispielsweise Ethanol, Butanol, Hexanol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Linoleylalkohol;
• - Alkylamidoaminen, z. B. Tego Amid® S 18 (Stearylamidopropyldimethylamin);
• - Aminosäuren und ihren Derivaten, z. B. Aminosäureamide, insbesondere Di-, Tri- oder Tetra-Peptide, Aminosäureester und/oder phosphorylierte Aminosäuren und/oder deren physiologisch verträglichen Salzen; wie beispielsweise Alanin, Arginin, Cystein, Glutamin, Glycin, Histidin, Lysin, Leucin, Ornithin, Isoleucin, Serin, Tyrosin, Tryptophan, Valin und Phenylalanin;
• - Peptiden, insbesondere Oligopeptiden, wie z. B. Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, wobei Peptide mit einer Masse M < 1000 besonders bevorzugt sind;
• - Polyhydroxyverbindungen; hierbei sind insbesondere zu nennen
  • - Zucker mit 5 und/oder 6 Kohlenstoffatomen, insbesondere als Mono- und/oder Oligosaccharide, beispielsweise Glucose, Fructose, Galactose, Lactose, Arabinose, Ribose, Xylose, Lyxose, Allose, Altrose, Mannose, Gulose, Idose, Talose und Sucrose und/oder deren Derivate, z. B. Etherderivate, Aminoderivate und/oder Acetylderivate wie acetylierte Glucose, z. B. Tetraacetylglucose, Pentaacetylglucose und/oder 2-Acetamido-2-desoxyglucose. Bevorzugte Zuckerbausteine sind Glucose, Fructose, Galactose, Allose, Lactose, Arabinose und Sucrose; Glucose, Galactose und Lactose sind besonders bevorzugt;
  • - Onsäuren, insbesondere Gluconsäure, Glucuronsäure;
  • - Polyole, wie z. B. Glucamine, Glycerin, Mono- oder Diglyceride, 2-Ethyl-1,3- hexandiol, 2-Hydroxymethylpropantriol, Glycole wie Ethylenglykol, Diethylenglykol, Triethylenglykol, Propylenglykol, Dipropylenglykol, 1,3- Butandiol;
  • - Polyhydroxysäuren, wie z. B. Pentahydroxyhexansäure, Tetrahydroxypentansäure und/oder deren Derivate, wie z. B. Ether, Ester und/oder Amide, z. B. Pentahydroxyhexansäureamid und/oder deren physiologisch verträglichen Salzen; weitere Beispiele: Zitronensäure, Äpfelsäure oder Weinsäure.
• - Silikone, wie z. B. Cyclomethicone (Octamethylcyclotetrasiloxan, Decamethylcyclopentasiloxan, Dodecamethylcyclohexasiloxan), Hexamethyldisiloxan, Dimethicon-Copolymere, Polysiloxane sowie quaternierte Polysiloxane;
• - Esterquats und/oder deren Derivate, z. B. Halogenide, Methylsulfate, wobei unter Esterquats quaternierte Estersalze von Fettsäuren z. B. mit Triethanolamin, mit Diethanolalkylaminen oder mit 1,2-Dihydroxypropyldialkylaminen verstanden werden; es kann bevorzugt sein, quaternierte Estersalze von linear und/oder verzweigten aliphatischen gesättigten und/oder ungesättigten C₁-C₂₀-Fettsäuren mit den o. g. Alkanolaminen einzusetzen
• - Pantolacton
• - Panthenol und/oder dessen Derivate;
• - weitere Vitamine, wie z. B. Vitamin B6, C und/oder E und/oder deren Derivate;
• - Hydroxysäuren, wie z. B. α-, β-Hydroxyfettsäuren bzw. Ketofeusäuren und/oder deren physiologisch verträglichen Salzen; wie beispielsweise Salicylsäure oder Milchsäure, Glyoxylsäure, Glycolsäure.

According to the invention, group P can preferably be derived from a number of compound classes, in particular from:

• linear and / or branched fatty acids, preferably C ₂ -C ₃₀ fatty acids, particularly preferably C ₄ -C ₁₈ fatty acids, most preferably C ₆ -C ₁₀ fatty acids and / or their physiologically tolerable salts; Further examples are derived from the carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, lactic acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, acic acid, sorbic acid, sorbic acid, sorbic acid, sorbic acid, sorbic acid, sorbic acid , Crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoyl acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, 4,4'-nicotinic acid, bicinic acid, bicinic acid, Dicyano-6,6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalenpentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazole carboxylic acid, gallic acid or propane tricarboxylic acid, and of the dicarboxylic acids selected from the group that is formed ch compounds of the general formula (II),
  
  
  in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH group and the other for hydrogen or a methyl or Ethyl radical, dicarboxylic acids of the general formula (II) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (II) by addition of a molecule of water to the double bond in the cyclohexene ring;
• linear and / or branched and saturated and / or unsaturated alcohols, preferably C ₂ -C ₃₀ alcohols, particularly preferably C ₄ -C ₂₄ alcohols, most preferably C ₆ -C ₂₂ alcohols; such as ethanol, butanol, hexanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol;
• Alkylamidoamines, e.g. B. Tego Amid® S 18 (stearylamidopropyldimethylamine);
• - Amino acids and their derivatives, e.g. B. amino acid amides, especially di-, tri- or tetra-peptides, amino acid esters and / or phosphorylated amino acids and / or their physiologically tolerable salts; such as alanine, arginine, cysteine, glutamine, glycine, histidine, lysine, leucine, ornithine, isoleucine, serine, tyrosine, tryptophan, valine and phenylalanine;
• - Peptides, especially oligopeptides, such as. B. protein hydrolyzates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, peptides with a mass M <1000 being particularly preferred;
• - polyhydroxy compounds; this should be mentioned in particular
  • - Sugar with 5 and / or 6 carbon atoms, in particular as mono- and / or oligosaccharides, for example glucose, fructose, galactose, lactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose and / or their derivatives, e.g. B. ether derivatives, amino derivatives and / or acetyl derivatives such as acetylated glucose, e.g. B. tetraacetylglucose, pentaacetylglucose and / or 2-acetamido-2-deoxyglucose. Preferred sugar components are glucose, fructose, galactose, allose, lactose, arabinose and sucrose; Glucose, galactose and lactose are particularly preferred;
  • - On acids, especially gluconic acid, glucuronic acid;
  • - Polyols, such as B. glucamines, glycerol, mono- or diglycerides, 2-ethyl-1,3-hexanediol, 2-hydroxymethylpropane triol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol;
  • - Polyhydroxy acids, such as. B. pentahydroxyhexanoic acid, tetrahydroxypentanoic acid and / or their derivatives, such as. B. ethers, esters and / or amides, e.g. B. pentahydroxyhexanoic acid amide and / or its physiologically tolerable salts; further examples: citric acid, malic acid or tartaric acid.
• - Silicones, such as B. cyclomethicones (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane), hexamethyldisiloxane, dimethicone copolymers, polysiloxanes and quaternized polysiloxanes;
• - Esterquats and / or their derivatives, e.g. B. halides, methyl sulfates, wherein quaternized ester salts of fatty acids z. B. with triethanolamine, with diethanolalkylamines or with 1,2-dihydroxypropyldialkylamines; it may be preferred to use quaternized ester salts of linear and / or branched aliphatic saturated and / or unsaturated C ₁ -C ₂₀ fatty acids with the abovementioned alkanolamines
• - pantolactone
• - panthenol and / or its derivatives;
• - Other vitamins, such as B. Vitamin B6, C and / or E and / or their derivatives;
• - Hydroxy acids, such as. B. α-, β-hydroxy fatty acids or keto acids and / or their physiologically tolerable salts; such as salicylic acid or lactic acid, glyoxylic acid, glycolic acid.

Particularly preferred care substances, from which the care component P can be derived, in the context of the present invention are glucose, galactose, allose, lactose, Tetraacetylglucose, 2-acetamido-2-deoxyglucose, 2-hydroxymethylpropane triol and / or Pentahydroxyhexansäureamid.

As a rule, the care components P are so in terms of their size selected that these are to be treated with the colorant according to the invention Fibers can penetrate.

Multifunctional care components within the meaning of the present invention can different positions on the spacer 5 with one or more Dye components to be connected. So z. B. Monosaccharides over all Hydroxy groups are linked, e.g. B. at the 2- and / or 3-position.

• - einem Oxidationsfarbstoffvorprodukt vom Kuppler- oder Entwicklertyp,
• - einem Derivat des Indols oder Indolins als Vorläufer des Melanins,
• - einem direktziehenden Farbstoff,
• - Isatin und/oder Isatin-Derivaten und/oder
• - als Farbstoff und/oder Farbstoffvorprodukt geeigneten Carbonylverbindungen.

The group F preferably represents a group which is derived from

• an oxidant dye intermediate of the coupler or developer type,
• a derivative of indole or indoline as a precursor of melanin,
• - a direct dye,
• - Isatin and / or isatin derivatives and / or
• - Carbonyl compounds suitable as a dye and / or dye precursor.

According to a first, preferred embodiment of the present invention, conducts group F ab from a coupler type oxidation dye precursor.

As coupler components, m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are used.

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

Coupler components preferred according to the invention are:

• m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 3 -Amino-6-methoxy-2-methylaminophenol, 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-diamino benzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1 , 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
• - Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• - Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole;
• - pyrimidine derivatives;

• - Methylendioxybenzolderivate wie beispielsweise 3,4-Methylendioxyphenol, 1- Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'- Hydroxyethyl)-amino-3,4-methylendioxybenzol.

Preferred representatives are 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; such as

• - Methylenedioxybenzene derivatives such as 3,4-methylenedioxyphenol, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Coupler components preferred according to the invention are in particular 3-dimethylaminophenol, 2,4-dihydroxyaniline, 8-amino-6-methoxy-quinoline, 2-amino-5-naphthol-1,7- disulfonic acid, 3-amino-1-phenyl-5-pyrazolone, 3,5-diaminobenzamide, 3- Methylsulfonylamino-2-methylaniline, 5,6-dihydroxybenzimidazole, 2,2'- Dihydroxybenzylamine, 3,5,3 ', 5'-tetraamino-2,2'-dimethoxy-diphenyl, 3,5-diamino-p- chlorobenzotrifluoride, 4-methyl-3-aminophenol, 2,4-diamino-3-chlorophenol, 1-amino-3-di- (2-hydroxyethylamino) -4-ethoxybenzene, 2,4-dimethylresorcinol, bis- (2,4-diaminophenoxy) - methane, 2,6-bis (hydroxyethyl) pyridine, 4-hydroxy-3-methoxybenzyl alcohol, 8- Hydroxyquinoline, 4-hydroxy-3-methoxy-benzylamine, 4-ethylresorcinol, 2-methylthio-5- aminophenol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol, 2,6-dimethoxy-3- aminophenol and 2,6-diamino-3-methylthiotoluene, and in particular m-phenylenediamine, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 5-amino- 4-chloro-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro 6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6- Dihydroxy-3,4-dimethylpyridine, m-aminophenol, 2-chlororesorcinol, 5-β- Hydroxyethylamino-2-methylphenol, 2,4-diaminophenoxyethanol, 2-amino-4-β- hydroxyethylaminoanisole, 1,3-bis (2 ', 4'-diaminophenoxy) propane.

Regarding other coupler-type oxidation dye precursors, of which the Group F can continue to expressly refer to the well-known monographs, z. B. Ch. Zviak, The Science of Hair Care, Chapter 8 (pages 264-267), published as a volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in disk form from Federal Association of German Industry and Trade Companies for Medicines, Health and Personal Care Products e.V., Mannheim.

According to a second, likewise preferred, embodiment of the present Invention, group F is derived from an oxidation dye precursor Developers type.

Primary aromatic amines with a. Are usually used as developer components further, in the para or ortho position, free or substituted hydroxy or amino group, 1,2,4-phenylenetriamine, diaminopyridine derivatives, heterocyclic Hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.

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


in which
G ¹ 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 ( C ₁ to C ₄ ) alkyl radical, a 4'-aminophenyl radical and / 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 radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy ( C ₁ to C ₄ ) alkyl radical and / or a C ₁ to C ₄ alkyl radical which is substituted by a nitrogen-containing group;
G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₁ to C ₄ Hydroxyalkoxyradikal, a C ₁ - to C ₄ -Acetylaminoalkoxyradikal, a C ₁ - to C ₄ -Mesylaminoalkoxyradikal and / or a C ₁ - to C ₄ -Carbamoylaminoalkoxyradikal;
G ⁴ represents a hydrogen atom, a halogen atom and / or a C ₁ to C ₄ alkyl radical or
when G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo 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 / or butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ to C ₄ alkoxy radicals which are preferred according to the invention are, for example, a methoxy and / or an ethoxy group. Further preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl and / or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. Examples of halogen atoms according to the invention are F, Cl and / or Br atoms, and C ₁ atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ -Trialkylammoniumgruppen, C ₁ - to C ₄ - Monohydroxyalkylaminogruppen, imidazolinium and / or ammonium ,

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p- Phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p- phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5- Dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p- phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) - aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p- phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β- Hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl- 3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ- Dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl- p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β- Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, 4,4'-diaminodiphenylamine and / or 5,8-diaminobenzo-1,4-dioxane and their physiological tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 4,4'- Diaminodiphenylamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine and / or their physiologically acceptable salts.

According to the invention, it can also be preferred as the developer component To use compounds that contain at least two aromatic nuclei with Amino and / or hydroxyl groups are substituted.

• - die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• - die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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


in which:
Z ¹ and Z ² independently represent a hydroxyl or NH ₂ radical, which is optionally substituted by a C ₁ - to C ₄ substituted -Hydroxyalkylradikal and / or by a bridge Y -, -C ₄ alkyl radical by C ₁ or which is optionally part of a bridging ring system;
the bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear and / or branched alkylene chain and / or an alkylene ring, which is formed by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, and / or a direct bond;
G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ -Aminoalkyl radical and / or a direct connection to the bridging Y;
G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridging Y and / or a C ₁ - to C ₄ -alkyl radical,
with the provisos that

• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

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

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2- hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and / or 1,10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and / or one of them physiologically acceptable salts.

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


in which:
G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy (C ₁ - to C ₄₎ -alkylaminoradikal, a C ₁ - to C ₄ -Hydroxyalkoxyradikal, a C ₁ - to C ₄ hydroxyalkyl (C ₁ - to C ₄ ) -aminoalkyl radical and / or a (di- C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl radical;
G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy - (C ₁ to C ₄ ) alkyl radical, a C ₁ to C ₄ aminoalkyl radical and / or a C ₁ to C ₄ cyanoalkyl radical;
G ¹⁵ represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical and / or a benzyl radical; and or
G ¹⁶ represents hydrogen and / or a halogen atom.

According to the invention, the substituents used in formula (E3) are analogous to the above Executions defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N- Methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2- Hydroxymethylamino-4-amino-phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2- hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4- Amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β- hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4- Amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-chlorophenol, 4- Amino-2 - ((diethylamino) methyl) phenol and / or their physiologically acceptable salts.

Furthermore, the developer component can be selected from o-aminophenol and its Derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol and / or 2-amino-4-chlorophenol and / or their physiologically tolerable salts.

Furthermore, the developer component can be selected from heterocyclic Developer components such as the pyridine, pyrimidine, pyrazole, pyrazole Pyrimidine derivatives and / or their physiologically acceptable salts.

Preferred pyridine derivatives are especially the compounds described in the patents GB 1 026 978 and GB 1 153 196 can be described, such as 2,5-diamino-pyridine, 2- (4- Methoxyphenyl) amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (β- Methoxyethyl) amino-3-amino-6-methoxy-pyridine, 3,4-diamino-pyridine and / or their physiologically acceptable salts.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 23 59 399, the Japanese patent application JP 02019576 A2 and / 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, 2,5,6- Triaminopyrimidine and / or their physiologically acceptable salts.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 38 43 892, DE 41 33 957 and / or patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988 can be described, such as 4,5-diamino-1-methylpyrazole, 4,5- Diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1- phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5- hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1- methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β- hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1- ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5- Diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1- isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'- aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4 (β-hydroxyethyl) amino-1-methylpyrazole, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5 and / or their physiologically acceptable salts.

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


in which:
G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C 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 ) -alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical which can optionally be protected by an acetyl-ureide or sulfonyl radical , 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 links, a C ₁ - to C ₄ -hydroxyalkyl and / or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) - aminoalkyl radical;
the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -Hydroxyalkyladikal, a C ₂ - to C ₄ - Polyhydroxyalkylradikal, a C ₁ - to C ₄ aminoalkyl radical, 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, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl and / 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 and / 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,
n has the value 0 or 1,
with the proviso that
the sum of p + q is not equal to 0;
when p + q is 2, n is 0 and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);
if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7)

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

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

• - Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,5-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 2,7-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 3-Amino pyrazol-[1,5-a]-pyrimidin-7-ol;
• - 3-Amino pyrazol-[1,5-a]-pyrimidin-5-ol;
• - 2-(3-Amino pyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• - 2-(7-Amino pyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• - 2-[(3-Amino pyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 2-[(7-Amino pyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 5,6-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,6-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,5,N7,N7-Tetramethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomeres Gleichgewicht vorhanden ist. Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

• - pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethyl pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 3-amino pyrazol- [1,5-a] pyrimidin-7-ol;
• - 3-amino pyrazol- [1,5-a] pyrimidin-5-ol;
• - 2- (3-amino pyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-amino pyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-Amino pyrazol- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-Amino pyrazol- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;
• - 5,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,5, N7, N7-tetramethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

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

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

Particularly preferred oxidation dye precursors of the developer type, of which in the context of the present invention, the dye component F can be derived z. B. p-phenylenediamine, p-tolylenediamine, 1,2,4-phenylenetriamine, 2- (β-hydroxyethyl) -p- phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, p-aminophenol, 3-methyl p-aminophenol, 2-aminomethyl-p-aminophenol, 2-N, N-diethylaminomethyl-p- aminophenol, bis (2-hydroxy-5-aminophenyl) methane, 2,5-diaminopyridine, 2,4,5,6- Tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine and 1- (β-hydroxyethyl) -4,5- diaminopyrazole.

Regarding other developer type oxidation dye precursors, of which the Group F can continue to expressly refer to the well-known monographs, z. B. Ch. Zviak, The Science of Hair Care, Chapter 8 (pages 264-267), published as a volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in disk form from Federal Association of German Industry and Trade Companies for Medicines, Health and Personal Care Products e. V., Mannheim, referred to.

According to a third preferred embodiment of the present invention, conducts group F ab from a precursor of melanin selected from the derivatives of Indols and Indolins, as well as their physiologically acceptable salts. As part of the In the present invention, "precursors of melanin" include such derivatives of indole and indoline, which are able to undergo an oxidative process Training melanin dyes or corresponding melanin dye derivatives.

According to the invention, preference is given to indoles and indolines in the context of this embodiment, which has at least one hydroxy and / or amino group, preferably as a substituent on Six ring. These groups can carry further substituents, e.g. B. in the form of a Etherification or esterification of the hydroxy group or an alkylation of the Amino group. Indoles and indolines with two of these groups, especially two Hydroxy groups, one or both of which may be etherified or esterified particularly preferred.

Derivatives of indoline, such as 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, 5-hydroxyindoline, 6-hydroxyindoline, 5-aminoindoline, 6-aminoindoline and / or 4-aminoindoline.

Derivatives of 5,6-dihydroxyindoline of the formula (IIIa) are very particularly preferred,


in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group or a C ₃ -C ₆ cycloalkyl group;
R ² represents hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation;
R ³ represents hydrogen or a C ₁ -C ₄ alkyl group;
R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which
R ⁶ represents a C ₁ -C ₄ alkyl group or an optionally substituted phenyl group, and / or
R ⁵ stands for one of the groups mentioned under R ⁴ .

Preferred representatives according to the invention are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline. The basic body, the 5,6-dihydroxyindoline, is very special prefers.

Preferred indoles according to the invention, from which the group F is derived 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, 5- Hydroxyindole, 6-hydroxyindole, 5-aminoindole, 6-aminoindole and 4-aminoindole.

Derivatives of 5,6-dihydroxyindole of the formula (IIIb) are particularly preferred,


in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group or a C ₃ -C ₆ cycloalkyl group,
R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
R ³ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CH ₂ -NR ⁷ R ⁸ , in which R ⁷ and R ⁸ independently of one another represent hydrogen or a C ₁ -C ₄ alkyl group,
R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which
R ⁶ represents a C ₁ -C ₄ alkyl group or an optionally substituted phenyl group, and
R ⁵ stands for one of the groups mentioned under R ⁴ .

Preferred representatives according to the invention are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole. The main body, the 5,6-dihydroxyindole, is very particularly preferred.

According to a fourth, preferred, embodiment of the present invention Group F deviates from direct dyes.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 known compounds as well as 2,4- Dinitroaniline, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) - aminophenol, 4-methyl-2-nitroaniline, N- (1-allyl) -2-nitro-1,4-phenylenediamine, 3-nitro-4- pyrrolidin-1-ylanilin, 4-acetylamino-2-nitroaniline, 2-amino-5-nitropyridine, 2-nitro-p- phenylenediamine, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, 1- (2'- Hydroxyethyl) amino-4-methyl-2-nitrobenzene, picramic acid, 2-amino-6-chloro-4- nitrophenol, 4-ethylamino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid, 4- Amino-3,5-dinitrobenzonitrile, 2,6-dinitro-4-trifluoromethylaniline, 4,5-diamino-3- nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The Dye component F can preferably differ from cationic direct dyes, which are sold under the Arianor® trademark.

Furthermore, the agents according to the invention can also occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and contain alkanna root.

According to a fifth preferred embodiment of the present invention, conducts group F ab of isatin and / or isatin derivatives.

In addition to isatin itself, a number of isatin derivatives come into consideration.
Particularly suitable derivatives are: isatin derivatives of the formula (IVa)

in which
R ^{1 represents} hydrogen, a C ₁ -C ₄ alkyl group, a C ₂ -C ₄ hydroxyalkyl group, a C ₂ -C ₂₀ acyl group, a phenyl group, a benzoyl group, a hydroxy group, one optionally with C ₁ -C ₄ - Alkyl or phenyl-substituted amino group, a C ₂ -C ₈ alkenyl, dihydroxy (C ₃ -C ₆ ) alkyl, trihydroxy (C ₄ -C ₆ ) alkyl, tetrahydroxy (C ₅ - C ₆ ) alkyl, pentahydroxy-C ₆ alkyl, C ₂ -C ₄ aminoalkyl, C ₁ -C ₄ sulfoalkyl group, a 2-furfurylmethyl-, 2-thienylmethyl optionally substituted with C ₁ -C ₄ -alkyl -, 2-pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl radical or an aralkyl group of the formula (IVb)


in which R ⁶ and R ⁷ independently of one another represent hydrogen, halogen, hydroxyl or amino groups, which may optionally be substituted by C ₁ -C ₄ alkyl or phenyl, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ - Alkoxy groups, carboxy groups or sulfo groups and R ^{8 represents} hydrogen, a C ₁ -C ₄ alkyl group or a C ₂ -C ₄ hydroxyalkyl group and x denotes 0, 1 or 2; and
R ² , R ³ , R ⁴ and R ⁵ independently of one another denote hydrogen, hydroxy, halogen, nitro groups, sulfo groups, carboxyl groups, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups or NR ⁹ R ¹⁰ groups, where R ⁹ and R ^{10 are} independently hydrogen; Represent C ₁ -C ₄ alkyl groups or C ₂ -C ₄ hydroxyalkyl groups, and two adjacent groups R ³ , R ⁴ and R ^{5 can} also represent an alkylenedioxy group having 1 to 4 C atoms; and their physiologically tolerable salts. Isatin derivatives of the formula (IVc)

in the
R ¹ and R ² independently of one another are hydrogen, hydroxy, halogen, C ₁ -C ₄ -alkyl groups, hydroxy- (C ₁ -C ₄ ) -alkyl, tert.-amino- (C ₁ -C ₄ ) -alkyl-, C ₁ -C ₄ alkoxy groups, nitro groups, sulfo groups, carboxyl groups, or NR ³ R ⁴ groups, where R ³ and R ⁴ independently of one another are hydrogen; Represent C ₁ -C ₄ alkyl groups or C ₁ -C ₄ hydroxyalkyl groups; and
Y represents a hydroxy group, a (C ₁ -C ₄ ) alkoxy group or an amino group which can be replaced by (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) - alkyl, carboxy (C ₁ -C ₄ ) alkyl, sulfo (C ₁ -C ₄ ) alkyl or hydroxy (C ₁ -C ₄ ) alkyl groups substituted or part of a heterocyclic 5-, 6- or Can be 7-ring, and their physiologically acceptable salts.

Further isatin derivatives, such as those in the published patent applications DE 44 09 143, DE 43 14 317 and WO 98 47 472 can be described.

According to a sixth preferred embodiment of the present invention I group F from suitable as a dye and / or dye precursor arbonylverbindungen.

• - 2-Oxoessigsäurederivate der Formel (Va) wie sie in der Offenlegungsschrift DE 44 17 546 beschrieben werden
  
  
  in der
  R¹ und R² unabhängig voneinander für Wasserstoffatome, Halogenatome, C₁-C₄- Alkylgruppen, C₁-C₄-Alkanoylgruppen, C₁-C₄-Alkoxygruppen, Nitro-, Hydroxy-, Sulfo-, Carboxyl- oder NR⁴R⁵-Gruppen stehen, wobei R⁴ und R⁵ unabhängig voneinander Wasserstoffatome oder C₁-C₄-Alkylgruppen bedeuten, und
  R³ für Wasserstoff, eine C₁-C₄-Alkylgruppe, eine Arylgruppe, eine Hydroxygruppe, eine gegebenenfalls mit C₁-C₄-Alkyl oder Aryl substituierte Aminogruppe, eine C₁-C₄-Alkanoylgruppe, eine Arenoylgruppe, eine C₃-C₈-Alkenylgruppe, eine Mono- oder Dihydroxy-C₂-C₆- alkylgruppe, eine Amino-C₁-C₄-alkylgruppe, eine Sulfo-C₁-C₄-alkylgruppe, eine Carboxy-C₁-C₄-alkylgruppe, eine 2-Furyl-, 2- Furfurylmethyl-, 2-Thienylmethyl-, 3-Pyridylmethyl- oder 4-Pyridylmethylgruppe oder für eine Gruppe der Formel (Vb),
  
  
  steht, in der R⁶ und R⁷ unabhängig voneinander Wasserstoffatome, Halogenatome, Hydroxygruppen, mit C₁-C₄-Alkyl oder Aryl substituierte Aminogruppen, C₁-C₄- Alkylgruppen, C₁-C₄-Alkoxygruppen, Carboxygruppen, Sulfogruppen bedeuten, R₈ für Wasserstoff eine C₁-C₄-Alkylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe steht und x für 0, 1 oder 2 steht, sowie deren physiologisch verträgliche Salze;
• - Tropolone der Formel (VI) wie sie m der Offenlegungsschrift DE 197 17 225 beschrieben werden
  
  
  in der
  R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für Wasserstoff, Halogen oder (C₁-C₄)- Alkyl bedeuten, wobei die Reste R¹ und R² auch gemeinsam einen an die Doppelbindung ankondensierten Benzolring, der seinerseits durch Hydroxy-, (C₁- C₄)-Alkyl- (C₁-C₄)-Alkoxygruppen oder Halogenatome substituiert sein kann, bilden können, und deren physiologisch verträglichen Salze;
• - Heterocyclischen Carbonylverbindungen mit der Formel (VII) und deren physiologisch verträglichen Salze wie sie in der Offenlegungsschrift EP 87 37 44 beschrieben werden
  
  
  in der
  Het für einen 5-, 6- oder 7-gliedrigen, gesättigten oder ungesättigten Heterocyclus mit 1 bis 3 Heteroatomen, die ausgewählt sein können aus N, O und S, der benzokondensiert und/oder substituiert sein kann durch Halogen, (C₁-C₄)-Alkyl-, (C₁-C₄)-Alkoxy-, Hydroxy-(C₁-C₄)-alkyl-, Carboxy-(C₁-C₄)-alkyl-, Hydroxy-, Oxo-, tert-Amino-, Nitro-, Carboxy- oder Sulfogruppen, und z. B. ein Pyrrolyl-, Indolyl-, Carbazolyl-, Pyridinyl-, Chinolinyl-, Isochinolinyl-, Aridinyl-, Pyridazinyl-, Pyrimidinyl-, Pyrazinyl-, Chinoxalinyl-, Pyrazolyl-, Imidazolyl-, Thiazolyl-, Oxazolyl-, Pyridoxalyl-, Pyrrolidinyl-, Piperidinyl-, Furyl-, Thienyl-, Benzimidazolyl-, Benzoxazolyl-, Benzothiazolyl-, s-Triazinyl-, Benzofuryl-, Chromanyl-, Dibenzofuryl- und/oder Indazolylrest sein kann;
  X für eine direkte Bindung oder eine Vinylengruppe steht,
  R¹ für ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, die durch Halogenatome, (C₁- C₄)-Alkoxy-, (C₁-C₄)-Acyl- oder Hydroxy-(C₁-C₄)-alkylgruppen substituiert sein kann, steht;
• - Keto- und/oder Aldehydverbindungen, vorzugsweise ausgewählt aus der Gruppe aus aromatischen und heteroaromatischen Aldehyden und Ketonen wie sie in der Offenlegungsschrift EP 87 37 45 beschrieben werden, insbesondere 1,3- Carbonylverbindungen, 1,2-Diketone, Ninhydrin und dessen Derivate, Alloxan, Isobarbitursäure, Aminoacroleinderivate, p- und o-Chinon-Derivaten, z. B. Glutaconaldehyd, 1-Formyl-3-hydroxymethylen-1-cyclohexen, 1-Formyl-3- hydroxymethylen-1-cyclohepten und 7-Hydroxy-2,4,6-heptatrienal und deren substituierten Derivate sowie deren physiologisch verträgliche Salze;
• - Aminovinylaldehyde oder -ketone der Formel (VIII) oder deren Derivate wie sie in der Offenlegungsschrift EP 87 37 46 beschrieben werden
  
  
  in der
  R¹ und R² unabhängig voneinander ein Wasserstoffatom, eine (C₁-C₄)-Alkylgruppe, eine Hydroxy-(C₁-C₄)-alkylgruppe, eine Phenylgruppe, die substituiert sein kann, oder gemeinsam mit dem N-Atom einen heterocyclischen Ring bilden, bedeuten,
  R³, R⁴, R⁵, R⁶ und R⁷ unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₄)- Alkylgruppe oder ein Halogenatom stehen, und
  x 0, 1 oder 2 bedeutet, wobei R⁶ und R⁷ sowie R⁴ und R⁶, wenn x gleich 1 ist, jeweils gemeinsam einen Ring bilden können.
  Geeignete Aminovinylaldehyde oder -ketone stellen beispielsweise 3-Aminoacrolein, 3-Dimethylaminoacrolein, 4-Dimethylamino-3-buten-2-on, 5-Dimethylamino-2,4- pentadienal, 5-Diethylamino-2,4-pentadienal, 5-N-Methylanilino-2,4-pentadienal, 5- Pyrrolidino-2,4-pentadienal, 5-Piperidino-2,4-pentadienal, 5-Morpholino-2,4- pentadienal, 5-Dimethylamino-2-methyl-2,4-pentadienal, 5-Dimethylamino-3-methyl- 2,4-pentadienal, 5-Dimethylamino-4-methyl-2,4-pentadienal, 5-Dimethylamino-3,5- dimethyl-2,4-pentadienal, 5-Dimethylamino-3-chlor-2,4-pentadienal, 6- Dimethylamino-3,5-hexadien-2-on 7-Dimethylamino-2,4,6-heptatrienal, 7- Morpholino-2,4,6-heptatrienal, 3-Dimethylaminomethylen-2-chlor-1-formyl-1- cyclohexen, 3-Dimethylaminomethylen-1-formyl-1-cyclopenten und deren physiologisch verträglichen Salze dar;
• - Benzylidenketone mit der Formel (IX) wie in der Offenlegungsschrift EP 87 37 43 beschrieben
  
  
  in der
  R¹, R² und R³ ein Wasserstoff-, ein Halogenatom, eine (C₁-C₄) Alkyl-, Hydroxy-(C₁- C₄)-alkyl-, tert. Amino-(C₁-C₄)-alkyl-, (C₁-C₄)-Alkoxy-, eine Aminogruppe, die durch eine (C₁-C₄)-Alkyl- oder Hydroxy-(C₁-C₄)-alkylgruppe substituiert oder Bestandteil eines heterocyclischen 5-, 6- oder 7-Ringes sein kann, eine Nitro-, Carboxy-, Sulfogruppe,
  R⁴ ein Wasserstoffatom, eine niedere (C_1-4) Alkyl-, (C_1-4)-Acylgruppe und
  R⁵ einen C₁-C₄-Alkylrest, wobei R⁴ und R⁵ auch gemeinsam für einen Alkylenrest mit 1 bis 5 C-Atomen in der Kette, der durch C_1-4-Alkyl-, Hydroxy-, Oxo- oder Hydroxy-(C₁-C₄)-alkylrest substituiert sein kann, stehen können, bedeuten;
  geeignete Vertreter für Verbindungen der Formel (IX) sind beispielsweise Benzylidenaceton, 4-Hydroxybenzylidenaceton, 2-Hydroxybenzylidenaceton, 4- Methoxybenzylidenaceton, 4-Hydroxy-3-methoxybenzylidenaceton, 4- Dimethylaminobenzylidenaceton, 3,4-Methylendioxybenzylidenaceton, 4- Pyrrolidinobenzylidenaceton, 4-Piperidinobenzylidenaceton, 4- Morpholinobenzylidenaceton, 4-Diethylaminobenzylidenaceton, 3-Benzyliden-2,4- pentandion, 3-(4-Hydroxybenzyliden)-2,4-pentandion, 3-(4-Dimethylaminobenzyliden)-2,4-pentandion, 2-Benzylidencyclohexanon, 2-(4- Hydroxybenzyliden)-cyclohexanon, 2-(4-Dimethylaminobenzyliden)- cyclohexanon, 3-Benzyliden-1,3-cyclohexandion, 3-(4-Hydroxybenzyliden)-1,3- cyclohexandion, 3-(4-Dimethylamino-benzyliden)-1,3-cyclohexandion, 3- Benzyliden-5,5-dimethyl-1,3-cyclohexandion, 3-(4-Hydroxybenzyliden)-5,5- dimethyl-1,3-cyclohexandion, 3-(4-Hydroxy-3-methoxybenzyliden)-5,5-dimethyl- 1,3-cyclohexandion, 3-(4-Dimethylamino-benzyliden)-5,5-dimethyl-1,3- cyclohexandion, 2-Benzyliden-cyclopentanon, 2-(4-Hydroxybenzyliden)- cyclopentanon, 2-(4-Dimethylamino-benzyliden)-cyclopentanon, wobei 4- Dimethylamino-benzylidenaceton, (1-(Dimethylaminophenyl)-but-1-en-3-on), 3,4- Methylendioxy-benzylidenaceton, 4-Hydroxybenzylidenaceton und 3-(4-Hydroxy- 3-methoxybenzyliden)-5,5-dimethyl-1,3-cyclohexandion sowie deren physiologisch verträgliche Salze;
• - ungesättigte Aldehyde mit der Formel (X) wie sie in der Offenlegungsschrift WO 98 47 473 beschrieben werden
  
  
  in der
  R¹, R², R³ und R⁴ unabhängig voneinander für Wasserstoff, Halogen, einen C₁-C₄- Alkoxy-, C₁-C₄-Alkyl-, Aryl- oder C₁-C₄-Alkoxy-C₁-C₄-Alkylrest und
  x für die Zahlen 1 oder 2 stehen, wobei R¹ und R², R¹ und R³, R² und R³ sowie R² und R⁴ jeweils zusammen mit dem Restmolekül einen 5- bis 7-gliedrigen Ring bilden können, wenn x gleich 1 ist, sowie die entsprechenden Mono-, Bis- bzw. omega- Alkoxyacetale, beispielsweise Glutaconaldehyd, 1-Formyl-3-hydroxymethylen-1- cyclohexen, 1-Formyl-3-hydroxymethylen-1-cyclohepten und 7-Hydroxy- 2,4,6- heptatrienal und deren Derivate sowie deren physiologisch verträgliche Salze.

A number of connections can be considered here. Carbonyl compounds which are particularly suitable according to the invention are:

• - 2-Oxoacetic acid derivatives of the formula (Va) as described in published patent application DE 44 17 546
  
  
  in the
  R ¹ and R ² independently of one another for hydrogen atoms, halogen atoms, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkanoyl groups, C ₁ -C ₄ alkoxy groups, nitro, hydroxyl, sulfo, carboxyl or NR ⁴ R ⁵ groups, where R ⁴ and R ⁵ independently of one another denote hydrogen atoms or C ₁ -C ₄ alkyl groups, and
  R ^{3 represents} hydrogen, a C ₁ -C ₄ alkyl group, an aryl group, a hydroxy group, an amino group which is optionally substituted by C ₁ -C ₄ alkyl or aryl, a C ₁ -C ₄ alkanoyl group, an arenoyl group, a C ₃ -C ₈ alkenyl group, a mono- or dihydroxy-C ₂ -C ₆ -alkyl group, an amino-C ₁ -C ₄ -alkyl group, a sulfo-C ₁ -C ₄ -alkyl group, a carboxy-C ₁ -C ₄ alkyl group, a 2-furyl, 2-furfurylmethyl, 2-thienylmethyl, 3-pyridylmethyl or 4-pyridylmethyl group or for a group of the formula (Vb),
  
  
  is in which R ⁶ and R ^{7 are} independently hydrogen atoms, halogen atoms, hydroxyl groups, amino groups substituted by C ₁ -C ₄ alkyl or aryl, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, carboxy groups, sulfo groups R _{8 represents} hydrogen, a C ₁ -C ₄ alkyl group or a C ₂ -C ₆ hydroxyalkyl group and x represents 0, 1 or 2, and the physiologically tolerated salts thereof;
• - Tropolones of the formula (VI) as described in DE 197 17 225
  
  
  in the
  R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are hydrogen, halogen or (C ₁ -C ₄ ) - alkyl, the radicals R ¹ and R ² also together being a benzene ring fused to the double bond, which in turn may be substituted by hydroxy, (C ₁ -C ₄ ) alkyl (C ₁ -C ₄ ) alkoxy groups or halogen atoms, and their physiologically tolerable salts;
• - Heterocyclic carbonyl compounds with the formula (VII) and their physiologically tolerable salts as described in published patent application EP 87 37 44
  
  
  in the
  Het for a 5-, 6- or 7-membered, saturated or unsaturated heterocycle having 1 to 3 heteroatoms, which can be selected from N, O and S, which can be benzo-fused and / or substituted by halogen, (C ₁ -C ₄ ) -alkyl-, (C ₁ -C ₄ ) -alkoxy-, hydroxy- (C ₁ -C ₄ ) -alkyl-, carboxy- (C ₁ -C ₄ ) -alkyl-, hydroxy-, oxo-, tert -Amino, nitro, carboxy or sulfo groups, and z. B. a pyrrolyl, indolyl, carbazolyl, pyridinyl, quinolinyl, isoquinolinyl, aridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinoxalinyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, pyridoxalyl , Pyrrolidinyl, piperidinyl, furyl, thienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, s-triazinyl, benzofuryl, chromanyl, dibenzofuryl and / or indazolyl radical;
  X represents a direct bond or a vinylene group,
  R ^{1 represents} a hydrogen atom, a (C ₁ -C ₆ ) alkyl group which is substituted by halogen atoms, (C ₁ - C ₄ ) alkoxy, (C ₁ -C ₄ ) acyl or hydroxy (C ₁ -C ₄ ) alkyl groups may be substituted;
• Keto and / or aldehyde compounds, preferably selected from the group consisting of aromatic and heteroaromatic aldehydes and ketones as described in published patent application EP 87 37 45, in particular 1,3-carbonyl compounds, 1,2-diketones, ninhydrin and its derivatives, Alloxan, isobarbituric acid, aminoacroline derivatives, p- and o-quinone derivatives, e.g. B. glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy-2,4,6-heptatrienal and their substituted derivatives and their physiologically acceptable salts;
• - Aminovinyl aldehydes or ketones of the formula (VIII) or their derivatives as described in published patent application EP 87 37 46
  
  
  in the
  R ¹ and R ² independently of one another are a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, a hydroxy (C ₁ -C ₄ ) alkyl group, a phenyl group which may be substituted, or one together with the N atom form heterocyclic ring, mean
  R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ independently of one another represent a hydrogen atom, a (C ₁ -C ₄ ) alkyl group or a halogen atom, and
  x denotes 0, 1 or 2, where R ⁶ and R ⁷ and R ⁴ and R ⁶ , when x is 1, can each together form a ring.
  Suitable aminovinyl aldehydes or ketones are, for example, 3-aminoacrolein, 3-dimethylaminoacrolein, 4-dimethylamino-3-buten-2-one, 5-dimethylamino-2,4-pentadienal, 5-diethylamino-2,4-pentadienal, 5-N -Methylanilino-2,4-pentadienal, 5-pyrrolidino-2,4-pentadienal, 5-piperidino-2,4-pentadienal, 5-morpholino-2,4-pentadienal, 5-dimethylamino-2-methyl-2,4 -pentadienal, 5-dimethylamino-3-methyl-2,4-pentadienal, 5-dimethylamino-4-methyl-2,4-pentadienal, 5-dimethylamino-3,5-dimethyl-2,4-pentadienal, 5-dimethylamino -3-chloro-2,4-pentadienal, 6- dimethylamino-3,5-hexadien-2-one 7-dimethylamino-2,4,6-heptatrienal, 7- morpholino-2,4,6-heptatrienal, 3- Dimethylaminomethylene-2-chloro-1-formyl-1-cyclohexene, 3-dimethylaminomethylene-1-formyl-1-cyclopentene and their physiologically tolerable salts;
• - Benzylidenketone with the formula (IX) as described in the published patent application EP 87 37 43
  
  
  in the
  R ¹ , R ² and R ^{3 are} a hydrogen atom, a halogen atom, a (C ₁ -C ₄ ) alkyl, hydroxy (C ₁ - C ₄ ) alkyl, tert. Amino (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, an amino group which is substituted by a (C ₁ -C ₄ ) alkyl or hydroxy (C ₁ -C ₄ ) alkyl group can be substituted or can be part of a heterocyclic 5-, 6- or 7-ring, a nitro, carboxy, sulfo group,
  R ^{4 is} a hydrogen atom, a lower (C _1-4 ) alkyl, (C _1-4 ) acyl group and
  R ^{5 is} a C ₁ -C ₄ alkyl radical, where R ⁴ and R ⁵ also together for an alkylene radical with 1 to 5 carbon atoms in the chain, which is C _1-4 alkyl, hydroxy, oxo or hydroxy - (C ₁ -C ₄ ) -alkyl may be substituted, may be;
  Suitable representatives for compounds of the formula (IX) are, for example, benzylidene acetone, 4-hydroxybenzylidene acetone, 2-hydroxybenzylidene acetone, 4-methoxybenzylidene acetone, 4-hydroxy-3-methoxybenzylidene acetone, 4-dimethylaminobenzylidene acetone, 3,4-methylenedioxybenzylidene acetone, 4-pyrrolidinobenzidone-4-pyrrolidinobenzene-4-pyridolidinobenzyl-piperacetonidyl-4-pyridolidinobenzyl-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzyl-4-pyrrolidinobenzyl-4 , 4-morpholinobenzylidene acetone, 4-diethylaminobenzylidene acetone, 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, 3-benzylidene-1,3-cyclohexanedione, 3- (4-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4- Dimethylamino-benzylidene) -1,3-cyclohexanedione, 3-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 3- (4-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 3- ( 4-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 3- (4-dimethylamino-benzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- Benzylidene-cyclopentanone, 2- (4-hydroxybenzylidene) - cyclopentanone, 2- (4-dimethylamino-benzylidene) -cyclopentanone, where 4-dimethylamino-benzylidene acetone, (1- (dimethylaminophenyl) -but-1-en-3-one) , 3,4-methylenedioxy-benzylidene acetone, 4-hydroxybenzylidene acetone and 3- (4-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione and their physiologically acceptable salts;
• - Unsaturated aldehydes with the formula (X) as described in the published patent application WO 98 47 473
  
  
  in the
  R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, halogen, a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, aryl or C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl and
  x stands for the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ^{4 can} each form a 5- to 7-membered ring together with the rest of the molecule, if x is 1, and the corresponding mono-, bis- or omega-alkoxyacetals, for example glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy- 2,4,6-heptatrienal and its derivatives and their physiologically tolerable salts.

The spacer group S of the formula (I) can be a structural element which has a common one Is part of groups P and F. In the simplest case, it is Structural element around an atom, which is a common component of groups P and F, the atom is preferably an O, N, S, C or P atom. Especially it is preferably a structural element containing O or N.

Furthermore, S in the structural formula (I) can also stand for a direct bond or for at least one spacer group. If there are several spacer groups, for example two spacer groups, these are preferably independently unsubstituted and / or substituted alkylene groups, each of which is preferably terminal Attack nitrogen atom (s) or oxygen atom (s) of groups P and F.

• - Alkylengruppen der allgemeinen Formel -C_nH_2n, insbesondere -(CH₂)_n-, in denen n für eine ganze Zahl, insbesondere eine Zahl von 1 bis 8 und ganz besonders bevorzugt für eine Zahl von 1 bis 4, steht;
  erfindungsgemäß bevorzugte Alkylengruppen sind die Methylen-, 1,2-Ethylen- und 1,3-Propylen-Gruppe;
• - Cycloaliphatische Gruppen wie Cyclopentyl-, Cyclohexyl- und Cycloheptylgruppen;
• - Mono- und Polyhydroxyalkylengruppen der allgemeinen Formel -C_nH_2n-x(OH)_x, in denen n für eine ganze Zahl, insbesondere eine Zahl von 1 bis 8 und ganz besonders bevorzugt für eine Zahl von 1 bis 4, steht und x für eine ganze Zahl, insbesondere für eine Zahl von 1 bis 3, steht;
  bevorzugte Hydroxyalkylengruppen sind die Hydroxymethylen-, die Hydroxy-1,2- ethylen-, die 2-Hydroxy-1,3-propylen, die 2,3-Dihydroxy-1,3-propylen- und die 2,3- Dihydroxy-1,4-butylen-Gruppe;
• - gegebenenfalls an den Alkylketten substituierte Dialkylenaminogruppen, insbesondere solche der allgemeinen Formel -(CH₂)_n-N(Z)-(CH₂)_m-, in der n und m unabhängig voneinander für eine ganze Zahl von 1 bis 8, insbesondere von 1 bis 4, stehen können, jedoch bevorzugt für die gleiche Zahl stehen, und Z für Wasserstoff, eine C_1-8-, insbesondere C_1-4-Alkylgruppe, eine C_1-8-, insbesondere C_1-4- Monohydroxyalkylgruppe, eine C_2-8-, insbesondere C_2-4-Dihydroxyalkylgruppe oder eine eine C_3-8-, insbesondere C_3-4-Trihydroxyalkylgruppe steht,
  sowie solche der allgemeinen Formel
  
  
  in der a und b unabhängig voneinander für ganze Zahlen von 0 bis 4 und c und d für 0 oder 1 stehen mit der Maßgabe, daß c = 0 ist, wenn a = 0 ist und d = 0 ist, wenn b = 0 ist, n für eine ganze Zahl von 1 bis 5 und m für eine ganze Zahl von 1 bis 3 steht mit der Maßgabe, daß die Summe n+m 3 bis 8 ist. Besonders bevorzugt ist die 1,4-Piperazinogruppe;
• - unabhängig voneinander für eine ganze Zahl von 1 bis 8, insbesondere von 1 bis 4, stehen können, n und m jedoch bevorzugt für die gleiche Zahl stehen, und Z und A unabhängig voneinander für Wasserstoff, eine C_1-8-, insbesondere C_1-4-Alkylgruppe, eine C_1-8-, insbesondere C_1-4-Monohydroxyalkylgruppe, eine C_2-8-, insbesondere C_2-4- Dihydroxyalkylgruppe oder eine eine C_3-8-, insbesondere C_3-4-Trihydroxyalkylgruppe stehen;
• - gegebenenfalls an den Alkylketten substituierte Ethergruppen, insbesondere solche der allgemeinen Formel -(CH₂)_n-O-(CH₂)_m-, in der n und m unabhängig voneinander für eine ganze Zahl von 1 bis 8, insbesondere von 1 bis 4, stehen können, jedoch bevorzugt für die gleiche Zahl stehen;
• - gegebenenfalls an den Alkylketten substituierte Polyethergruppen, insbesondere solche der allgemeinen Formel -(CH₂)_n-O-(CH₂)_m-O-(CH₂)_m-O-(CH₂)_n-, in der n und m unabhängig voneinander für eine ganze Zahl von 1 bis 8, insbesondere von 1 bis 4, stehen können, jedoch bevorzugt für die gleiche Zahl stehen;
• - schwefelhaltige Gruppen, insbesondere Gruppen der allgemeinen Formel -(CH₂)_n-S(O)_o-(CH₂)_m-, in der n und m unabhängig voneinander für eine ganze Zahl von 1 bis 8, insbesondere von 1 bis 4, stehen können, jedoch bevorzugt für die gleiche Zahl stehen, und o für 0, 1 oder 2 steht.

Preferred spacer groups S are:

• - Alkylene groups of the general formula -C _n H _2n , in particular - (CH ₂ ) _n -, in which n is an integer, in particular a number from 1 to 8 and very particularly preferably a number from 1 to 4;
  Alkylene groups preferred according to the invention are the methylene, 1,2-ethylene and 1,3-propylene group;
• - Cycloaliphatic groups such as cyclopentyl, cyclohexyl and cycloheptyl groups;
• - Mono- and polyhydroxyalkylene groups of the general formula -C _n H _2n-x (OH) _x , in which n is an integer, in particular a number from 1 to 8 and very particularly preferably a number from 1 to 4, and x represents an integer, in particular a number from 1 to 3;
  preferred hydroxyalkylene groups are the hydroxymethylene, the hydroxy-1,2-ethylene, the 2-hydroxy-1,3-propylene, the 2,3-dihydroxy-1,3-propylene and the 2,3-dihydroxy-1 , 4-butylene group;
• - Dialkylene amino groups optionally substituted on the alkyl chains, in particular those of the general formula - (CH ₂ ) _n -N (Z) - (CH ₂ ) _m -, in which n and m independently of one another for an integer from 1 to 8, in particular from 1 to 4, can, but preferably stand for the same number, and Z represents hydrogen, a C _1-8 -, in particular C _1-4 -alkyl group, a C _1-8 -, in particular C _1-4 - monohydroxyalkyl group, a C _2-8 -, in particular C _2-4 -dihydroxyalkyl group or a C _3-8 -, in particular C _3-4 -trihydroxyalkyl group,
  as well as those of the general formula
  
  
  in which a and b independently of one another represent integers from 0 to 4 and c and d stand for 0 or 1, with the proviso that c = 0 if a = 0 and d = 0 if b = 0, n stands for an integer from 1 to 5 and m stands for an integer from 1 to 3 with the proviso that the sum n + m is 3 to 8. The 1,4-piperazino group is particularly preferred;
• - independently of one another can be an integer from 1 to 8, in particular from 1 to 4, but n and m are preferably the same number, and Z and A independently of one another are hydrogen, a C _1-8 -, in particular C. _1-4 alkyl group, a C _1-8 , especially C _1-4 monohydroxyalkyl group, a C _2-8 , especially C _2-4 dihydroxyalkyl group or a C _3-8 , especially C _3-4 Trihydroxyalkyl group;
• ether groups optionally substituted on the alkyl chains, in particular those of the general formula - (CH ₂ ) _n -O- (CH ₂ ) _m -, in which n and m independently of one another for an integer from 1 to 8, in particular from 1 to 4 , can stand, but preferably stand for the same number;
• - Polyether groups optionally substituted on the alkyl chains, in particular those of the general formula - (CH ₂ ) _n -O- (CH ₂ ) _m -O- (CH ₂ ) _m -O- (CH ₂ ) _n -, in which n and m can independently represent an integer from 1 to 8, in particular from 1 to 4, but preferably stand for the same number;
• - Sulfur-containing groups, in particular groups of the general formula - (CH ₂ ) _n -S (O) _o - (CH ₂ ) _m -, in which n and m independently of one another for an integer from 1 to 8, in particular from 1 to 4 , can stand, but preferably stand for the same number, and o stands for 0, 1 or 2.

The spacers S are free in the hybrid dyes according to the invention via their two Bonds linked to the groups P and F so that they each as a substituent on the Instead of a hydrogen atom of the molecules that underlie groups P and F. lie.

According to a first preferred embodiment, the spacer group 5 occurs as a substituent in place of a hydrogen atom of a primary or secondary amino group, the directly or via an aliphatic hydrocarbon group to an aliphatic, cycloaliphatic, aromatic or heterocyclic system is bound.

According to a second preferred embodiment, the spacer group S occurs as Substitute in place of the hydrogen atom of a hydroxyl group, directly or via an aliphatic hydrocarbon group to an aliphatic, cycloaliphatic, aromatic or heterocyclic system is bound.

Caring agents are particularly preferred in the context of the present invention Hybrid dyes and / or hybrid dye precursors in which S is an N or O atom containing structural element, which is a common component of groups P and F.

Furthermore, the care components P of the care hybrid dyes and / or hybrid dye precursors of the formula (I) contained in the colorants according to the invention

P - (S - F) _x (I)

several groups SF are bound. x can represent an integer from 1 to 3, 1 and 2 being particularly preferred.

Most suitable caring hybrid dyes and / or hybrid dye precursors which can be used in the colorants according to the invention are listed below: 2-deoxy-2- (2,4-dinitrophenylamino) -α, β-D-glucopyranose

P derived from glucose
F derived from a direct puller (2,4-dinitroaniline)
S stands for an N-structural element, which is the common component of the groups P and F 2- (4-carboxy-2,6-dinitrophenylamino) -2-deoxy-α, β-D-glucopyranose

P derived from glucose
F derived from a direct puller (4-amino-3,5-dinitrobenzoic acid)
S stands for an N-structural element, which is the common component of the groups P and F 2- (6-amino-4-carboxy-2-nitrophenylamino) -2-deoxy-α, β-D-glucopyranose

P derived from glucose
F derived from a direct puller (4,5-diamino-3-nitrobenzoic acid)
S stands for an N-structural element, which is the common component of the groups P and F 2- (4-cyano-2,6-dinitrophenylamino) -2-deoxy-α, β-D-glucopyranose

P derived from glucose
F derived from a direct puller (4-amino-3,5-dinitrobenzonitrile)
S stands for an N-structural element, which is the common component of the groups P and F 2-deoxy-2- (2,4-dinitrophenylamino) -1-O-methyl-α, β-D-glucopyranose

P derived from 1-O-methyl-glucose
F derived from a direct puller (2,4-dinitroaniline)
S stands for an N-structural element, which is the common component of the groups P and F 2-deoxy-2- (2,4-dinitrophenylamino) -1-O-ethyl-α, β-D-glucopyranose

P derived from 1-O-ethyl-α, β-D-glucose
F derived from a direct puller (2,4-dinitroaniline)
S stands for an N-structural element, which is the common component of the groups P and F 1-O- (4-aminophenyl) -α, β-D-glucopyranose

P derived from glucose
F derived from a developer (p-aminophenol)
S stands for an O-structural element, which is the common component of the groups P and F 1-O- (4-methyl-2-nitrophenylaminoethyl) -α, β-D-glucopyranose

P derived from glucose
F derived from a direct puller (4-methyl-2-nitroaniline)
S represents an ethylene group 1-O- (4-methyl-2-nitrophenylaminoethyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranose

P derived from tetra-O-acetylglucose
F derived from a direct puller (4-methyl-2-nitroaniline)
S stands for an ethylene group N- (4-allylamino-3-nitrophenyl) -α, β-D-glucopyranosylamine

P derived from glucose
F derived from a direct puller (N- (1-allyl) -2-nitro-1,4-phenylenediamine)
S stands for an N-structural element, which is the common component of the groups P and F N- (4-aminophenyl) -α, β-D-glucopyranosylamine

P derived from glucose
F derived from a developer (p-phenylenediamine)
S stands for an N-structural element, which is the common component of the groups P and F N- (5-aminopyrid-2-yl) -α, β-D-glucopyranosylamine hydrochloride

P derived from glucose
F derived from a developer (2,5-diaminopyridine)
S stands for an N-structural element, which is the common component of the groups P and F N- (4-hydroxyphenyl) -α, β-D-glucopyranosylamine

P derived from glucose
F derived from a developer (4-aminophenol)
S stands for an N-structural element, which is the common component of the groups P and F N- (4-allylamino-3-nitrophenyl) -2-acetamido-2-deoxy-α, β-D-glucopyranosylamine

P derived from 2-acetamido-2-deoxyglucose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structural element, which is the common component of the groups P and F N- (4-allylamino-3-nitrophenyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranosylamine

P derived from tetra-O-acetylglucose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structural element which is the common constituent of the groups P and F N- (3-nitro-4-pyrrolidin-1-yl-phenyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranosyl amine

P derived from tetra-O-acetylglucose
F derived from a direct puller (3-nitro-4-pyrrolidin-1-ylanilin)
S stands for an N-structural element, which is the common component of the groups P and F N- (4-allylamino-3-nitrophenyl) -α, β-D-ga1actopyranosylamine

P derived from galactose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structural element, which is the common component of the groups P and F N- (4-hydroxyphenyl) -α, β-D-galactopyranosylamine

P derived from galactose
F derived from a developer (4-aminophenol)
S stands for an N-structural element, which is the common component of the groups P and F N- (4-allylamino-3-nitrophenyl) -α, β- (4-β-D-galactopyranosyl) -D-glucopyranosylamine

P derived from lactose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for in N structural element, which is the common component of the groups P and F N- (3-aminophenyl) -α, β- (4-β-D-galactopyranosyl) -D-glucopyranosylamine

P derived from lactose
F derived from a coupler (m-phenylenediamine)
S stands for an N structural element which is the common constituent of the groups P and F N- (4-allylamino-3-nitrophenylamino) -2-deoxy-2- (2,4-dinitrophenylamino) -α, β-D- glucopyranose

P derived from glucose
F each derived from direct pullers (2,4-dinitroaniline, N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structural element, which is the common component of groups P and F;
x is 2 2- (2,4-dinitrophenylamino) -2-hydroxymethylpropane-1,3-diol

P derived from 2-hydroxymethylpropane-1,3-diol
F derived from a direct puller (2,4-dinitroaniline)
S stands for an N-structural element, which is the common component of groups P and F 2- (2,4-diaminophenylamino) -2-hydroxymethylpropane-1,3-diol hydrochloride

P derived from 2-hydroxymethylpropane-1,3-diol
F derived from a developer (1,2,4-phenylenetriamine)
S stands for an N-structural element, which is the common component of groups P and F 2,3,4,5,6-pentahydroxyhexanoic acid (2- (2,4-dinitrophenylamino) ethyl) amide

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (2,4-dinitroaniline)
S represents an ethylene group 2,3,4,5,6-pentahydroxyhexanoic acid (2- (4-acetylamino-2-nitrophenylamino) ethyl) amide

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (4-acetylamino-2-nitroaniline)
S represents an ethylene group 2,3,4,5,6-pentahydroxyhexanoic acid (2- (5-nitropyridin-2-ylamino) ethyl) amide

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (2-amino-5-nitropyridine)
S represents an ethylene group 2,3,4,5,6-pentahydroxyhexanoic acid (2- (4-amino-2-nitrophenylamino) ethyl) amide

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (2-nitro-p-phenylenediamine)
S stands for an ethylene group

The most preferred among those listed above in those of the present invention Coloring agents that can be used as nurturing hybrid dyes and / or Hybrid dye precursors are 2- (2,4-dinitrophenylamino) -2- hydroxymethylpropane-1,3-diol, 2- (2,4-diaminophenylamino) -2-hydroxymethylpropane- 1,3-diol hydrochloride, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (2,4- dinitrophenylamino) ethyl) amide, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (4-acetylamino-2- nitrophenylamino) ethyl) amide, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (5-nitropyridine-2- ylamino) ethyl) amide, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (4-amino-2- nitrophenylamino) ethyl) amide, N- (4-allylamino-3-nitrophenyl) -2,3,4,6-O-tetraacetyl-α, β- D-glucopyranosylamine, N- (3-nitro-4-pyrrolidin-1-yl-phenyl) -2,3,4,6-O-tetraacetyl-α, β-D- glucopyranosylamine, N- (4-allylamino-3-nitrophenyl) -α, β-D-glucopyranosylamine, N- (4- Allylamino-3-nitrophenyl) -α, β- (4-β-D-galactopyranosyl) -D-glucopyranosylamine, N- (4- Allylamino-3-nitrophenyl) -α, β-D-galactopyranosylamine, 2- (6-amino-4-carboxy-2- nitrophenylamino) -2-deoxy-α, β-D-glucopyranose, 2- (4-cyano-2,6-dinitrophenylamino) - 2-deoxy-α, β-D-glucopyranose, 2- (4-carboxy-2,6-dinitrophenylamino) -2-deoxy-α, β-D- glucopyranose, N- (4-allylamino-3-nitrophenyl) -2-acetamido-2-deoxy-α, β-D- glucopyranosylamine, 1-O- (4-methyl-2-nitrophenylaminoethyl) -α, β-D-glucopyranose and N- (5-aminopyrid-2-yl) -α, β-D-glucopyranosylamine hydrochloride.

The above connections are usually easily accessible. Regarding the Production of the caring hybrid dyes according to the invention and / or Hybrid dye precursors are specifically based on those listed in the examples Syntheses referenced.

Some of the compounds listed were according to literature regulations manufactured, e.g. B. 2-deoxy-2- (2,4-dinitrophenylamino) -α, β-D-glucopyranose and 2- Deoxy-2- (2,4-dinitrophenylamino) -1-O-ethyl-α, β-D-glucopyranose, which after or, in The case of 2-deoxy-2- (2,4-dinitrophenylamino) -1-O-ethyl-α, β-D-glucopyranose, analog synthesized according to P.F. Lloyd, B. Evans, R.J. Fielder, Carbohydrate Research 1969, 9, 467 were.

The colorants can be one or more of the aforementioned caring hybrid dyes and / or hybrid dye precursors.

In a further embodiment, one or more of the aforementioned can also be used Connections may not be included.

• - Aminosäurederivate der Formel (X), in denen eine Aminogruppe durch einen Aromaten substituiert ist:
  
  
  in der
  n eine ganze Zahl zwischen 0 und 11 ist,
  R Wasserstoff, eine Aminogruppe, eine lineare oder verzweigte, gesättigte oder ungesättigte C₁-C₆-Alkylgruppe oder eine Gruppe ausgewählt aus den folgenden Gruppen ist:
  
  
  wobei
  R' eine eine lineare oder verzweigte, gesättigte oder ungesättigte C₁-C₆- Alkylgruppe,
  n' eine ganze Zahl zwischen 1 und 6 darstellt,
  X einen Aromaten mit ein oder zwei Ringen darstellt, wobei die Ringe ein oder mehrere Heteroatome, ausgewählt aus S. N oder O enthalten können oder die Ringe wenigstens durch eine Gruppe -NHR" oder eine Hydroxygruppe in para- oder ortho-Position der aromatischen Gruppe X hinsichtlich der NH-Gruppe substituiert sein können, wobei die Gruppe R" Wasserstoff, eine lineare oder verzweigte, gesättigte oder ungesättigte, gegebenenfalls hydroxylierte C₁-C₆-Alkylgruppe darstellt;
  oder ihre durch Zugabe einer Säure gewonnenen Salze;
• - Chinone oder N-Halogenchinonimine oder N,N'-Dihalogenchinondümine oder gegebenenfalls substituierte Chinone oder Cyclohexenone oder Cyclohexadienone der folgenden Formeln:
  
  
  wobei
  R¹ bis R⁴ Wasserstoff oder Halogen oder Alkyl, Aralkyl oder Aryl bedeuten, wobei benachbarte Gruppen miteinander oder mit Chinonanil-N-halogenimiden verbunden sein können.

In a preferred embodiment, the agents according to the invention are free from at least one compound, preferably selected from the group comprising

• - Amino acid derivatives of the formula (X) in which an amino group is substituted by an aromatic:
  
  
  in the
  n is an integer between 0 and 11,
  R is hydrogen, an amino group, a linear or branched, saturated or unsaturated C ₁ -C ₆ alkyl group or a group selected from the following groups:
  
  
  in which
  R 'is a linear or branched, saturated or unsaturated C ₁ -C ₆ alkyl group,
  n 'represents an integer between 1 and 6,
  X represents an aromatic with one or two rings, wherein the rings can contain one or more heteroatoms selected from S. N or O or the rings at least through a group -NHR "or a hydroxy group in the para or ortho position of the aromatic group X can be substituted with respect to the NH group, the group R "being hydrogen, a linear or branched, saturated or unsaturated, optionally hydroxylated C ₁ -C ₆ -alkyl group;
  or their salts obtained by adding an acid;
• - Quinones or N-haloquinoneimines or N, N'-dihaloquinone dimins or optionally substituted quinones or cyclohexenones or cyclohexadienones of the following formulas:
  
  
  in which
  R ¹ to R ⁴ denote hydrogen or halogen or alkyl, aralkyl or aryl, it being possible for adjacent groups to be linked to one another or to quinonanil-N-haloimides.

• - N-Glykoside gegebenenfalls substituierter aromatischer Amine, insbesondere N- Glucoside, N-Lactoside, N-Fructoside des 4-Aminodiphenylamins, des 4-Amino-4'- methoxydiphenylamins, des Anilins, Xylidins, p-Phenylendiamins, p-Aminophenols, 1-Nitro-2,5-phenylendiamins, 1,4-Diamino-2-nitrobenzols, wenn die erfindungsgemäßen Mittel einen sauren oder neutralen pH-Wert aufweisen;
• - N-Glykamine gegebenenfalls substituierter aromatischer Mono- oder Polyamine, insbesondere N-Glukamine des 4-Aminodiphenylamins, 1,4-Diamino-2-nitrobenzols, 1-Nitro-2,5-phenylendiamins, wenn die erfindungsgemäßen Mittel einen sauren oder neutralen pH-Wert aufweisen.

In a further preferred embodiment, the agents according to the invention are free of at least one compound selected from the group if their pH is in acid or neutral

• - N-glycosides of optionally substituted aromatic amines, in particular N-glucosides, N-lactosides, N-fructosides of 4-aminodiphenylamine, 4-amino-4'-methoxydiphenylamine, aniline, xylidine, p-phenylenediamine, p-aminophenol, 1 -Nitro-2,5-phenylenediamine, 1,4-diamino-2-nitrobenzene when the agents according to the invention have an acidic or neutral pH;
• - N-Glykamines optionally substituted aromatic mono- or polyamines, in particular N-glucamines of 4-aminodiphenylamine, 1,4-diamino-2-nitrobenzene, 1-nitro-2,5-phenylenediamine, if the agents according to the invention have an acidic or neutral pH Value.

According to a special embodiment of the invention, it can be preferred that Dye component F not from the dye precursors of the developer type to be selected if the care component P is an amino acid and the spacer S a is a common structural element of P and F.

According to a further special embodiment, it can be preferred that Dye component F not of the direct puller type, in particular of the type previously used described quinones, N-haloquinone imines, N, N'-dihaloquinone dimins, Select cyclohexenones and cyclohexadienones if the care component P derived from a mono- or disaccharide and the spacer S a common one Structural element of P and F is.

According to a special embodiment, it can be preferred that Dye component F not from direct pullers or dye precursors from Select developer type if the care component P is of a mono- or Disaccharide derived and the spacer component S a common structural element of P and F is.

The agents according to the invention contain at least one nourishing hybrid dye and / or hybrid dye precursor of structure (I) usually in amounts of 0.01 % By weight - 10% by weight, based on the total colorant. Amounts of 0.05% by weight - 5 % By weight, in particular amounts of 0.1% by weight - 3% by weight, are preferred.

The colorants according to the invention preferably contain at least one further Dye, another dye intermediate of the coupler or developer type, an indole or Indoline derivative as a melanin precursor, a substantive dye, isatin and / or its derivatives and / or suitable as a dye and / or dye precursor Carbonyl compounds.

In a first embodiment, those colorants are particularly preferred which, in addition to at least one nourishing hybrid dye and / or hybrid dye precursor Structure (I) contain at least one oxidation dye precursor. This Oxidation dye precursors can be of the coupler type as well as of Be a developer type.

The developer type oxidation dye precursors include, for example, primary ones aromatic amines with a further free one in the para or ortho position or substituted hydroxy or amino group, diaminopyridine derivatives, 4- Aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives in Consideration.

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


in which
G ¹ 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 ( C ₁ to C ₄ ) alkyl radical, a 4'-aminophenyl radical and / 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 radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy ( C ₁ to C ₄ ) alkyl radical and / or a C ₁ to C ₄ alkyl radical which is substituted by a nitrogen-containing group;
G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₁ to C ₄ Hydroxyalkoxyradikal, a C ₁ - to C ₄ -Acetylaminoalkoxyradikal, a C ₁ - to C ₄ - Mesylaminoalkoxyradikal and / or a C ₁ - to C ₄ -Carbamoylaminoalkoxyradikal;
G ⁴ represents a hydrogen atom, a halogen atom and / or a C ₁ to C ₄ alkyl radical or
when G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo 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 / or butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ to C ₄ alkoxy radicals which are preferred according to the invention are, for example, a methoxy and / or an ethoxy group. Further preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl and / or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. Examples of halogen atoms according to the invention are F, Cl and / or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ -Trialkylammoniumgruppen, C ₁ - to C ₄ - Monohydroxyalkylaminogruppen, imidazolinium and / or ammonium ,

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p- Phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p- phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5- Dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p- phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) - aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p- phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β- Hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl- 3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ- Dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl- p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β- Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, 4,4'-diaminodiphenylamine and / or 5,8-diaminobenzo-1,4-dioxane and their physiological tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 4,4'- Diaminodiphenylamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine and / or their physiologically acceptable salts.

According to the invention, it can also be preferred as the developer component To use compounds that contain at least two aromatic nuclei with Amino and / or hydroxyl groups are substituted.

• - die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• - die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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


in which:
Z ¹ and Z ² independently represent a hydroxyl or NH ₂ radical, which is optionally substituted by a C ₁ - substituted hydroxyalkyl radical and / or by a bridge Y -, -C ₄ alkyl radical by a C ₁ - to C ₄ or which is optionally part of a bridging ring system;
the bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear and / or branched alkylene chain and / or an alkylene ring, which is formed by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms can be interrupted or terminated and possibly substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, and / or a direct bond;
G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ -Aminoalkyl radical and / or a direct connection to the bridging Y;
G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond for bridging Y and / or a C ₁ - to C ₄ -alkyl radical,
with the provisos that

• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

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

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2- hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and / or 1,10-bis- (2% 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and / or one of them physiologically acceptable salts.

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


in which:
G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) - alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy (C ₁ - to C ₄₎ -alkylaminoradikal, a C ₁ - to C ₄ -Hydroxyalkoxyradikal, a C ₁ - to C ₄ hydroxyalkyl (C ₁ - to C ₄ ) aminoalkyl radical and / or a (di-C ₁ to C ₄ alkylamino) - (C ₁ to C ₄ ) alkyl radical;
G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy - (C ₁ to C ₄ ) alkyl radical, a C ₁ to C ₄ aminoalkyl radical and / or a C ₁ to C ₄ cyanoalkyl radical;
G ¹⁵ represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical and / or a benzyl radical; and or
G ¹⁶ represents hydrogen and / or a halogen atom.

According to the invention, the substituents used in formula (E3) are analogous to the above Executions defined.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N- Methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2- Hydroxymethylamino-4-amino-phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2- hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4- Amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β- hydroxyethyl-aminomethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4- Amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-chlorophenol, 4- Amino-2 - ((diethylamino) methyl) phenol and / or their physiologically acceptable salts.

Furthermore, the developer component can be selected from o-aminophenol and its Derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol and / or 2-amino-4-chlorophenol and / or their physiologically tolerable salts.

Furthermore, the developer component can be selected from heterocyclic Developer components such as the pyridine, pyrimidine, pyrazole, pyrazole Pyrimidine derivatives and / or their physiologically acceptable salts.

Preferred pyridine derivatives are especially the compounds described in the patents GB 1 026 978 and GB 1 153 196 can be described, such as 2,5-diamino-pyridine, 2- (4- Methoxyphenyl) amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (β- Methoxyethyl) amino-3-amino-6-methoxy-pyridine, 3,4-diamino-pyridine and / or their physiologically acceptable salts.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 23 59 399, the Japanese patent application JP 02019576 A2 and / 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, 2,5,6- Triaminopyrimidine and / or their physiologically acceptable salts.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 38 43 892, DE 41 33 957 and / or patent applications WO 94/08969, WO 94/08970, EP-740931 and DE 195 43 988 can be described, such as 4,5-diamino-1-methylpyrazole, 4,5- Diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1- phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5- hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1- methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β- hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1- ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5- Diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1- isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'- aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4 (β-hydroxyethyl) amino-1-methylpyrazole, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5 and / or their physiologically acceptable salts.

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


in which:
G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C 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 ) -alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical which can optionally be protected by an acetyl-ureide or sulfonyl radical , 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 links, a C ₁ - to C ₄ -hydroxyalkyl and / or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) - aminoalkyl radical;
the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -Hydroxyalkyladikal, a C ₂ - to C ₄ - Polyhydroxyalkylradikal, a C ₁ - to C ₄ aminoalkyl radical, 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, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl and / 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 and / 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,
n has the value 0 or 1,
with the proviso that
the sum of p + q is not equal to 0;
when p + q is 2, n is 0 and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);
if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7).

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

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

• - Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,5-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 2,7-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 3-Amino pyrazol-[1,5-a]-pyrimidin-7-ol;
• - 3-Amino pyrazol-[1,5-a]-pyrimidin-5-ol;
• - 2-(3-Amino pyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• - 2-(7-Amino pyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• - 2-[(3-Amino pyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 2-((7-Amino pyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 5,6-Dimethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,6-Dimethyl pyrazol-(1,5-a]-pyrimidin-3,7-diamin;
• - 2,5, N7, N7-Tetramethyl pyrazol-[1,5-a]-pyrimidin-3,7-diamin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomeres Gleichgewicht vorhanden ist. Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

• - pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethyl pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 3-amino pyrazol- [1,5-a] pyrimidin-7-ol;
• - 3-amino pyrazol- [1,5-a] pyrimidin-5-ol;
• - 2- (3-amino pyrazole- [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-amino pyrazole- [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-Amino pyrazol- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - ((7-Amino pyrazol- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;
• - 5,6-dimethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethyl pyrazole- (1,5-a] pyrimidine-3,7-diamine;
• - 2,5, N7, N7-tetramethyl pyrazole- [1,5-a] pyrimidine-3,7-diamine;

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

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

In a second preferred embodiment come as others Dye-dye precursors Oxidation dye precursors of the coupler type, for example m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, Pyrazolones and m-aminophenol derivatives.

• - m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, 5-(2-Hydroxyethylamino)-2-methylphenol, 3-Amino-2-chlor-6-methylphenol, 2- Hydroxy-4-aminophenoxyethanol, 3-Amino-6-methoxy-2-methylaminophenol, 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-Anophenol und dessen Derivate,
• - m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4- Diaminophenoxyethanol, 1,3-Bis-(2,4-diaminophenoxy)-propan, 1-Methoxy-2- amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2,4-diaminophenyl)-propan, 2,6- Bis-(2-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)- aminobenzol,
• - o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• - Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5- Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4- Trihydroxybenzol,
• - Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3- hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6- methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4- methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5- Diamino-2,6-dimethoxypyridin,
• - Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7- Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• - Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• - Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• - Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• - Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7- Hydroxyindol;
• - Pyrimidinderivate;
  Bevorzugte Vertreter sind 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; sowie
• - Methylendioxybenzolderivate wie beispielsweise 3,4-Methylendioxyphenol, 1- Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'- Hydroxyethyl)-amino-3,4-methylendioxybenzol.

Couplers preferred according to the invention are:

• m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (2-hydroxyethylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 3 -Amino-6-methoxy-2-methylaminophenol, 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-anophenol and its derivatives,
• m-diamino benzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1 , 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
• - Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• - Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole;
• - pyrimidine derivatives;
  Preferred representatives are 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; such as
• - Methylenedioxybenzene derivatives such as 3,4-methylenedioxyphenol, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Further coupler components preferred according to the invention are furthermore 3-dimethylaminophenol, 2,4-dihydroxyaniline, 8-amino-6-methoxy-quinoline, 2-amino-5-naphthol-1,7- disulfonic acid, 3-amino-1-phenyl-5-pyrazolone, 3,5-diaminobenzamide, 3- Methylsulfonylamino-2-methylaniline, 5,6-dihydroxybenzimidazole, 2,2'- Dihydroxybenzylamine, 3,5,3 ', 5'-tetraamino-2,2'-dimethoxy-diphenyl, 3,5-diamino-p- chlorobenzotrifluoride, 4-methyl-3-aminophenol, 2,4-diamino-3-chlorophenol, 1-amino-3-di- (2-hydroxyethylamino) -4-ethoxybenzene, 2,4-dimethylresorcinol, bis- (2,4-diaminophenoxy) - methane, 2,6-bis (hydroxyethyl) pyridine, 4-hydroxy-3-methoxybenzyl alcohol, 8- Hydroxyquinoline, 4-hydroxy-3-methoxy-benzylamine, 4-ethylresorcinol, 2-methylthio-5- aminophenol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol, 2,6-dimethoxy-3- aminophenol and 2,6-diamino-3-methylthiotoluene.

Particularly preferred couplers for the purposes of the invention are m-phenylenediamine, 1- Naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 2-methyl-1-naphthol, 5-amino-2- methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3 - aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy- 3,4-dimethylpyridine, 6-methyl-1,2,3,4-tetrahydroquinoxaline, m-aminophenol, o- Aminophenol and 2-chlororesorcinol.

According to a third, preferred, embodiment of the present invention the agents according to the invention further dye components, which differ from one Derive precursors of melanin, selected from the derivatives of indole and indoline, as well as their physiologically tolerable salts.

In the context of the present invention, "precursors of melanin" are such Derivatives of indole and indoline understood in the context of an oxidative Are able to process melanin dyes or corresponding melanin dyes Train derivatives.

According to the invention, preference is given to indoles and indolines in the context of this embodiment, which has at least one hydroxy and / or amino group, preferably as a substituent on Six ring. These groups can carry further substituents, e.g. B. in the form of a Etherification or esterification of the hydroxy group or an alkylation of the Amino group. Indoles and indolines with two of these groups, especially two Hydroxy groups, one or both of which may be etherified or esterified particularly preferred.

Derivatives of indoline, such as 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, 5-hydroxyindoline, 6-hydroxyindoline, 5-aminoindoline, 6-aminoindoline and / or 4-aminoindoline.

Derivatives of 5,6-dihydroxyindoline of the formula (IIIa) are very particularly preferred,


in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group or a C ₃ -C ₆ cycloalkyl group;
R ² represents hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation;
R ³ represents hydrogen or a C ₁ -C ₄ alkyl group;
R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which
R ⁶ represents a C ₁ -C ₄ alkyl group or an optionally substituted phenyl group, and / or
R ⁵ stands for one of the groups mentioned under R ⁴ .

Preferred representatives according to the invention are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline. The basic body, the 5,6-dihydroxyindoline, is very special prefers.

Preferred indoles according to the invention, from which the group P is derived 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, 5- Hydroxyindole, 6-hydroxyindole, 5-aminoindole, 6-aminoindole and 4-aminoindole.

Derivatives of 5,6-dihydroxyindole of the formula (IIIb) are particularly preferred,


in the independently of each other
R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group or a C ₃ -C ₆ cycloalkyl group,
R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
R ³ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CH ₂ -NR ⁷ R ⁸ , in which R ⁷ and R ⁸ independently of one another represent hydrogen or a C ₁ -C ₄ alkyl group,
R ⁴ stands for hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C ₁ -C ₄ alkyl group or an optionally substituted phenyl group, and
R ⁵ stands for one of the groups mentioned under R ⁴ .

Preferred representatives according to the invention are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole. The main body, the 5,6-dihydroxyindole, is very particularly preferred.

According to a fourth preferred embodiment of the present invention the agents according to the invention additionally contain direct dyes.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 known compounds as well as 2,4- Dinitroaniline, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) - aminophenol, 4-methyl-2-nitroaniline, N- (1-allyl) -2-nitro-1,4-phenylenediamine, 3-nitro-4- pyrrolidin-1-ylanilin, 4-acetylamino-2-nitroaniline, 2-amino-5-nitropyridine, 2-nitro-p- phenylenediamine, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, 1- (2'- Hydroxyethyl) amino-4-methyl-2-nitrobenzene, picramic acid, 2-amino-6-chloro-4- nitrophenol, 4-ethylamino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid, 4- Amino-3,5-dinitrobenzonitrile, 2,6-dinitro-4-trifluoromethylaniline, 4,5-diamino-3- nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The cationic direct dyes sold under the Arianor® trademark, are particularly preferred direct dyes.

Furthermore, the agents according to the invention can also occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and contain alkanna root.

According to a fifth preferred embodiment of the present invention the agents according to the invention also dyes, which are derived from isatin and / or Derive isatin derivatives.

In addition to isatin itself, a number of isatin derivatives come into consideration. Particularly suitable derivatives are: isatin derivatives of the formula (IVa)

in which
R ^{1 represents} hydrogen, a C ₁ -C ₄ alkyl group, a C ₂ -C ₄ hydroxyalkyl group, a C ₂ -C ₂₀ acyl group, a phenyl group, a benzoyl group, a hydroxy group, one optionally with C ₁ -C ₄ - Alkyl or phenyl substituted amino group, a C ₂ -C ₈ alkenyl, dihydroxy (C ₃ -C ₆ ) alkyl, trihydroxy (C ₄ - C ₆ ) alkyl, tetrahydroxy (C ₅ -C ₆ ) -alkyl, pentahydroxy-C ₆ -alkyl, C ₂ -C ₄ aminoalkyl, C ₁ -C ₄ sulfoalkyl, optionally substituted with C ₁ -C ₄ alkyl-substituted 2- Furfurylmethyl-, 2-thienylmethyl, 2- Pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl radical or an aralkyl group of the formula (IVb)


in which R ⁶ and R ⁷ independently of one another represent hydrogen, halogen, hydroxyl or amino groups, which may optionally be substituted by C ₁ -C ₄ alkyl or phenyl, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ - Are alkoxy groups, carboxy groups or sulfo groups and R ^{8 is} hydrogen, a C ₁ -C ₄ alkyl group or a C ₂ -C ₄ hydroxyalkyl group and x is 0, 1 or 2; and
R ² , R ³ , R ⁴ and R ⁵ independently of one another denote hydrogen, hydroxy, halogen, nitro groups, sulfo groups, carboxyl groups, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups or NR ⁹ R ¹⁰ groups, where R ⁹ and R ^{10 are} independently hydrogen; Represent C ₁ -C ₄ alkyl groups or C ₂ -C ₄ hydroxyalkyl groups, and two adjacent groups R ³ , R ⁴ and R ^{5 can} also represent an alkylenedioxy group having 1 to 4 C atoms; and their physiologically tolerable salts. Isatin derivatives of the formula (IVc)

in the
R ¹ and R ² independently of one another are hydrogen, hydroxy, halogen, C ₁ -C ₄ -alkyl groups, hydroxy- (C ₁ -C ₄ ) -alkyl, tert.-amino- (C ₁ -C ₄ ) -alkyl-, C ₁ -C ₄ alkoxy groups, nitro groups, sulfo groups, carboxyl groups, or NR ³ R ⁴ groups, where R ³ and R ⁴ independently of one another are hydrogen; Represent C ₁ -C ₄ alkyl groups or C ₁ -C ₄ hydroxyalkyl groups; and
Y represents a hydroxy group, a (C ₁ -C ₄ ) alkoxy group or an amino group which can be replaced by (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) - alkyl, carboxy (C ₁ -C ₄ ) alkyl, sulfo (C ₁ -C ₄ ) alkyl or hydroxy (C ₁ -C ₄ ) alkyl groups substituted or part of a heterocyclic 5-, 6- or Can be 7-ring, and their physiologically acceptable salts.

Further isatin derivatives, such as those in the published patent applications DE 44 09 143, DE 43 14 317 and WO 98 47 472 can be described.

According to a sixth preferred embodiment of the present invention the agents according to the invention dyes and / or dye precursors, which differ from Derive carbonyl compounds.

• - 2-Oxoessigsäurederivaten der Formel (Va) wie sie in der Offenlegungsschrift DE 44 17 546 beschrieben werden
  
  
  in der
  R¹ und R² unabhängig voneinander für Wasserstoffatome, Halogenatome, C₁-C₄- Alkylgruppen, C₁-C₄-Alkanoylgruppen, C₁-C₄-Alkoxygruppen, Nitro-, Hydroxy-, Sulfo-, Carboxyl- oder NR⁴R⁵-Gruppen stehen, wobei R⁴ und R⁵ unabhängig voneinander Wasserstoffatome oder C₁-C₄-Alkylgruppen bedeuten, und
  R³ für Wasserstoff, eine C₁-C₄-Alkylgruppe, eine Arylgruppe, eine Hydroxygruppe, eine gegebenenfalls mit C₁-C₄-Alkyl oder Aryl substituierte Aminogruppe, eine C₁-C₄-Alkanoylgruppe, eine Arenoylgruppe, eine C₃-C₈-Alkenylgruppe, eine Mono- oder Dihydroxy-C₂-C₆-alkylgruppe, eine Amino-C₁-C₄-alkylgruppe, eine Sulfo-C₁-C₄-alkylgruppe, eine Carboxy-C₁-C₄-alkylgruppe, eine 2-Furyl-, 2- Furfurylmethyl-, 2-Thienylmethyl-, 3-Pyridylmethyl- oder 4-Pyridylmethylgruppe oder für eine Gruppe der Formel (Vb),
  
  
  steht, in der R⁶ und R⁷ unabhängig voneinander Wasserstoffatome, Halogenatome, Hydroxygruppen, mit C₁-C₄-Alkyl oder Aryl substituierte Aminogruppen, C₁-C₄- Alkylgruppen, C₁-C₄-Alkoxygruppen, Carboxygruppen, Sulfogruppen bedeuten,
  R⁸ für Wasserstoff eine C₁-C₄-Alkylgruppe oder eine C₂-C₆-Hydroxyalkylgruppe steht und x für 0, 1 oder 2 steht, sowie deren physiologisch verträgliche Salze;
• - Tropolone der Formel (VI) wie sie in der Offenlegungsschrift DE 197 17 225 beschrieben werden
  
  
  in der
  R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für Wasserstoff, Halogen oder (C₁-C₄)- Alkyl bedeuten, wobei die Reste R¹ und R² auch gemeinsam einen an die Doppelbindung ankondensierten Benzolring, der seinerseits durch Hydroxy-, (C₁- C₄)-Alkyl- (C₁-C₄)-Alkoxygruppen oder Halogenatome substituiert sein kann, bilden können, und deren physiologisch verträglichen Salze;
• - Heterocyclischen Carbonylverbindungen mit der Formel (VI) und deren physiologisch verträglichen Salze wie sie in der Offenlegungsschrift EP 87 37 44 beschrieben werden
  
  
  in der
  Het für einen 5-, 6- oder 7-gliedrigen, gesättigten oder ungesättigten Heterocyclus mit 1 bis 3 Heteroatomen, die ausgewählt sein können aus N, O und S, der benzokondensiert und/oder substituiert sein kann durch Halogen, (C₁-C₄)-Alkyl-, (C₁-C₄)-Alkoxy-, Hydroxy-(C₁-C₄)-alkyl-, Carboxy-(C₁-C₄)-alkyl-, Hydroxy-, Oxo-, tert-Amino-, Nitro-, Carboxy- oder Sulfogruppen, und z. B. ein Pyrrolyl-, Indolyl-, Carbazolyl-, Pyridinyl, Chinolinyl-, Isochinolinyl-, Aridinyl-, Pyridazinyl-, Pyrimidinyl-, Pyrazinyl-, Chinoxalinyl-, Pyrazolyl-, Imidazolyl-, Thiazolyl-, Oxazolyl-, Pyridoxalyl-, Pyrrolidinyl-, Piperidinyl-, Furyl-, Thienyl-, Benzimidazolyl-, Benzoxazolyl-, Benzothiazolyl-, s-Triazinyl-, Benzofuryl-, Chromanyl-, Dibenzofuryl- und/oder Indazolylrest sein kann;
  X für eine direkte Bindung oder eine Vinylengruppe steht,
  R¹ für ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, die durch Halogenatome, (C₁- C₄)-Alkoxy-, (C₁-C₄)-Acyl- oder Hydroxy-(C₁-C₄)-alkylgruppen substituiert sein kann, steht;
• - Keto- und/oder Aldehydverbindungen, vorzugsweise ausgewählt aus der Gruppe aus aromatischen und heteroaromatischen Aldehyden und Ketonen wie sie in der Offenlegungsschrift EP 87 37 45 beschrieben werden, insbesondere 1,3- Carbonylverbindungen, 1,2-Diketone, Ninhydrin und dessen Derivate, Alloxan, Isobarbitursäure, Aminoacroleinderivate, p- und o-Chinon-Derivaten, z. B. Glutaconaldehyd, 1-Formyl-3-hydroxymethylen-1-cyclohexen, 1-Formyl-3 - hydroxymethylen-1-cyclohepten und 7-Hydroxy-2,4,6-heptatrienal und deren substituierten Derivate sowie deren physiologisch verträgliche Salze;
• - Aminovinylaldehyde oder -ketone der Formel (VIII) oder deren Derivate wie sie in der Offenlegungsschrift EP 87 37 46 beschrieben werden
  
  
  in der
  R¹ und R² unabhängig voneinander ein Wasserstoffatom, eine (C₁-C₄)-Alkylgruppe, eine Hydroxy-(C₁-C₄)-alkylgruppe, eine Phenylgruppe, die substituiert sein kann, oder gemeinsam mit dem N-Atom einen heterocyclischen Ring bilden, bedeuten,
  R³, R⁴, R⁵, R⁶ und R⁷ unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₄)- Alkylgruppe oder ein Halogenatom stehen, und
  x 0, 1 oder 2 bedeutet, wobei R⁶ und R⁷ sowie R⁴ und R⁶, wenn x gleich 1 ist, jeweils gemeinsam einen Ring bilden können.
  Geeignete Aminovinylaldehyde oder -ketone stellen beispielsweise 3-Aminoacrolein, 3-Dimethylaminoacrolein, 4-Dimethylamino-3-buten-2-on, 5-Dimethylamino-2,4- pentadienal, 5-Diethylamino-2,4-pentadienal, 5-N-Methylanilino-2,4-pentadienal, 5- Pyrrolidino-2,4-pentadienal, 5-Piperidino-2,4-pentadienal, 5-Morpholino-2,4- pentadienal, 5-Dimethylamino-2-methyl-2,4-pentadienal, 5-Dimethylamino-3-methyl- 2,4-pentadienal, 5-Dimethylamino-4-methyl-2,4-pentadienal, 5-Dimethylamino-3,5- dimethyl-2,4-pentadienal, 5-Dimethylamino-3-chlor-2,4-pentadienal, 6- Dimethylamino-3,5-hexadien-2-on 7-Dimethylamino-2,4,6-heptatrienal, 7- Morpholino-2,4,6-heptatrienal, 3-Dimethylaminomethylen-2-chlor-1-formyl-1- cyclohexen, 3-Dimethylaminomethylen-1-formyl-1-cyclopenten und deren physiologisch verträglichen Salze dar;
• - Benzylidenketone mit der Formel (IX) wie in der Offenlegungsschrift EP 87 37 43 beschrieben
  
  
  in der R¹, R² und R³ ein Wasserstoff, ein Halogenatom, eine (C₁-C₄) Alkyl-, Hydroxy-(C₁- C₄)-alkyl-, tert. Amino-(C₁-C₄)-alkyl-, (C₁-C₄)-Alkoxy-, eine Aminogruppe, die durch eine (C₁-C₄)-Alkyl- oder Hydroxy-(C₁-C₄)-alkylgruppe substituiert oder Bestandteil eines heterocyclischen 5-, 6- oder 7-Ringes sein kann, eine Nitro-, Carboxy-, Sulfogruppe,
  R⁴ ein Wasserstoffatom, eine niedere (C_1-4) Alkyl-, (C_1-4)-Acylgruppe und
  R⁵ einen C₁-C₄-Alkylrest, wobei R⁴ und R⁵ auch gemeinsam für einen Alkylenrest mit 1 bis 5 C-Atomen in der Kette, der durch C_1-4-Alkyl-, Hydroxy-, Oxo- oder Hydroxy-(C₁-C₄)-alkylrest substituiert sein kann, stehen können, bedeuten;
  geeignete Vertreter für Verbindungen der Formel (IX) sind beispielsweise Benzylidenaceton, 4-Hydroxybenzylidenaceton, 2-Hydroxybenzylidenaceton, 4- Methoxybenzylidenaceton, 4-Hydroxy-3-methoxybenzylidenaceton, 4- Dimethylaminobenzylidenaceton,3,4-Methylendioxybenzylidenaceton, 4- Pyrrolidinobenzylidenaceton, 4-Piperidinobenzylidenaceton, 4- Morpholinobenzylidenaceton, 4-Diethylaminobenzylidenaceton, 3-Benzyliden-2,4- pentandion, 3-(4-Hydroxybenzyliden)-2,4-pentandion, 3-(4-Dimethylaminobenzyliden)-2,4-pentandion, 2-Benzylidencyclohexanon, 2-(4- Hydroxybenzyliden)-cyclohexanon, 2-(4-Dimethylaminobenzyliden)- cyclohexanon, 3-Benzyliden-1,3-cyclohexandion, 3-(4-Hydroxybenzyliden)-1,3- cyclohexandion, 3-(4-Dimethylamino-benzyliden)-1,3-cyclohexandion, 3- Benzyliden-5,5-dimethyl-1,3-cyclohexandion, 3-(4-Hydroxybenzyliden)-5,5- dimethyl-1,3-cyclohexandion, 3-(4-Hydroxy-3-methoxybenzyliden)-5,5-dimethyl- 1,3-cyclohexandion, 3-(4-Dimethylamino-benzyliden)-5,5-dimethyl-1,3- cyclohexandion, 2-Benzyliden-cyclopentanon, 2-(4-Hydroxybenzyliden)- cyclopentanon, 2-(4-Dimethylamino-benzyliden)-cyclopentanon, wobei 4- Dimethylamino-benzylidenaceton, (1-(Dimethylaminophenyl)-but-1-en-3-on), 3,4- Methylendioxy-benzylidenaceton, 4-Hydroxybenzylidenaceton und 3-(4-Hydroxy- 3-methoxybenzyliden)-5,5-dimethyl-1,3-cyclohexandion sowie deren physiologisch verträgliche Salze;
• - ungesättigte Aldehyde mit der Formel (X) wie sie in der Offenlegungsschrift WO 98 47 473 beschrieben werden
  
  
  in der
  R¹, R², R³ und R⁴ unabhängig voneinander für Wasserstoff, Halogen, einen C₁-C₄- Alkoxy-, C₁-C₄-Alkyl-, Aryl- oder C₁-C₄-Alkoxy-C1 -C₄-Alkylrest und
  x für die Zahlen 1 oder 2 stehen, wobei R¹ und R², R¹ und R³, R² und R³ sowie R² und R⁴ jeweils zusammen mit dem Restmolekül einen 5- bis 7-gliedrigen Ring bilden können, wenn x gleich 1 ist, sowie die entsprechenden Mono-, Bis- insbesonders w-Bis-Alkoxyacetale, beispielsweise Glutaconaldehyd, 1-Formyl-3- hydroxymethylen-1-cyclohexen, 1-Formyl-3-hydroxymethylen-1-cyclohepten und 7-Hydroxy- 2,4,6-heptatrienal und deren Derivate sowie deren physiologisch verträgliche Salze.

A number of connections can be considered here. Carbonyl compounds which are particularly suitable according to the invention are:

• - 2-Oxoacetic acid derivatives of the formula (Va) as described in published patent application DE 44 17 546
  
  
  in the
  R ¹ and R ² independently of one another for hydrogen atoms, halogen atoms, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkanoyl groups, C ₁ -C ₄ alkoxy groups, nitro, hydroxyl, sulfo, carboxyl or NR ⁴ R ⁵ groups, where R ⁴ and R ⁵ independently of one another denote hydrogen atoms or C ₁ -C ₄ alkyl groups, and
  R ^{3 represents} hydrogen, a C ₁ -C ₄ alkyl group, an aryl group, a hydroxy group, an amino group which is optionally substituted by C ₁ -C ₄ alkyl or aryl, a C ₁ -C ₄ alkanoyl group, an arenoyl group, a C ₃ -C ₈ alkenyl group, a mono- or dihydroxy-C ₂ -C ₆ -alkyl group, an amino-C ₁ -C ₄ -alkyl group, a sulfo-C ₁ -C ₄ -alkyl group, a carboxy-C ₁ -C ₄ alkyl group, a 2-furyl, 2-furfurylmethyl, 2-thienylmethyl, 3-pyridylmethyl or 4-pyridylmethyl group or for a group of the formula (Vb),
  
  
  is in which R ⁶ and R ^{7 are} independently hydrogen atoms, halogen atoms, hydroxyl groups, amino groups substituted by C ₁ -C ₄ alkyl or aryl, C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, carboxy groups, sulfo groups .
  R ^{8 represents} hydrogen, a C ₁ -C ₄ alkyl group or a C ₂ -C ₆ hydroxyalkyl group and x represents 0, 1 or 2, and their physiologically tolerable salts;
• - Tropolones of formula (VI) as described in published patent application DE 197 17 225
  
  
  in the
  R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are hydrogen, halogen or (C ₁ -C ₄ ) - alkyl, the radicals R ¹ and R ² also together being a benzene ring fused to the double bond, which in turn may be substituted by hydroxy, (C ₁ -C ₄ ) alkyl (C ₁ -C ₄ ) alkoxy groups or halogen atoms, and their physiologically tolerable salts;
• - Heterocyclic carbonyl compounds with the formula (VI) and their physiologically tolerable salts as described in published patent application EP 87 37 44
  
  
  in the
  Het for a 5-, 6- or 7-membered, saturated or unsaturated heterocycle having 1 to 3 heteroatoms, which can be selected from N, O and S, which can be benzo-fused and / or substituted by halogen, (C ₁ -C ₄ ) -alkyl-, (C ₁ -C ₄ ) -alkoxy-, hydroxy- (C ₁ -C ₄ ) -alkyl-, carboxy- (C ₁ -C ₄ ) -alkyl-, hydroxy-, oxo-, tert -Amino, nitro, carboxy or sulfo groups, and z. B. a pyrrolyl, indolyl, carbazolyl, pyridinyl, quinolinyl, isoquinolinyl, aridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinoxalinyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, pyridoxalyl, Pyrrolidinyl, piperidinyl, furyl, thienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, s-triazinyl, benzofuryl, chromanyl, dibenzofuryl and / or indazolyl radical;
  X represents a direct bond or a vinylene group,
  R ^{1 represents} a hydrogen atom, a (C ₁ -C ₆ ) alkyl group which is substituted by halogen atoms, (C ₁ - C ₄ ) alkoxy, (C ₁ -C ₄ ) acyl or hydroxy (C ₁ -C ₄ ) alkyl groups may be substituted;
• Keto and / or aldehyde compounds, preferably selected from the group consisting of aromatic and heteroaromatic aldehydes and ketones as described in published patent application EP 87 37 45, in particular 1,3-carbonyl compounds, 1,2-diketones, ninhydrin and its derivatives, Alloxan, isobarbituric acid, aminoacroline derivatives, p- and o-quinone derivatives, e.g. B. glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3 - hydroxymethylene-1-cycloheptene and 7-hydroxy-2,4,6-heptatrienal and their substituted derivatives and their physiologically acceptable salts;
• - Aminovinyl aldehydes or ketones of the formula (VIII) or their derivatives as described in published patent application EP 87 37 46
  
  
  in the
  R ¹ and R ² independently of one another are a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, a hydroxy (C ₁ -C ₄ ) alkyl group, a phenyl group which may be substituted, or one together with the N atom form heterocyclic ring, mean
  R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ independently of one another represent a hydrogen atom, a (C ₁ -C ₄ ) alkyl group or a halogen atom, and
  x denotes 0, 1 or 2, where R ⁶ and R ⁷ and R ⁴ and R ⁶ , when x is 1, can each together form a ring.
  Suitable aminovinyl aldehydes or ketones are, for example, 3-aminoacrolein, 3-dimethylaminoacrolein, 4-dimethylamino-3-buten-2-one, 5-dimethylamino-2,4-pentadienal, 5-diethylamino-2,4-pentadienal, 5-N -Methylanilino-2,4-pentadienal, 5-pyrrolidino-2,4-pentadienal, 5-piperidino-2,4-pentadienal, 5-morpholino-2,4-pentadienal, 5-dimethylamino-2-methyl-2,4 -pentadienal, 5-dimethylamino-3-methyl-2,4-pentadienal, 5-dimethylamino-4-methyl-2,4-pentadienal, 5-dimethylamino-3,5-dimethyl-2,4-pentadienal, 5-dimethylamino -3-chloro-2,4-pentadienal, 6- dimethylamino-3,5-hexadien-2-one 7-dimethylamino-2,4,6-heptatrienal, 7- morpholino-2,4,6-heptatrienal, 3- Dimethylaminomethylene-2-chloro-1-formyl-1-cyclohexene, 3-dimethylaminomethylene-1-formyl-1-cyclopentene and their physiologically tolerable salts;
• - Benzylidenketone with the formula (IX) as described in the published patent application EP 87 37 43
  
  
  in which R ¹ , R ² and R ^{3 are} hydrogen, a halogen atom, a (C ₁ -C ₄ ) alkyl-, hydroxy- (C ₁ - C ₄ ) -alkyl-, tert. Amino (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, an amino group which is substituted by a (C ₁ -C ₄ ) alkyl or hydroxy (C ₁ -C ₄ ) alkyl group can be substituted or can be part of a heterocyclic 5-, 6- or 7-ring, a nitro, carboxy, sulfo group,
  R ^{4 is} a hydrogen atom, a lower (C _1-4 ) alkyl, (C _1-4 ) acyl group and
  R ^{5 is} a C ₁ -C ₄ alkyl radical, where R ⁴ and R ⁵ also together for an alkylene radical with 1 to 5 carbon atoms in the chain, which is C _1-4 alkyl, hydroxy, oxo or hydroxy - (C ₁ -C ₄ ) -alkyl may be substituted, may be;
  Suitable representatives for compounds of the formula (IX) are, for example, benzylidene acetone, 4-hydroxybenzylidene acetone, 2-hydroxybenzylidene acetone, 4-methoxybenzylidene acetone, 4-hydroxy-3-methoxybenzylidene acetone, 4-dimethylaminobenzylidene acetone, 3,4-methylenedioxybenzylidene acetone, 4-pyrrolidinobenzidone-4-pyrrolidinobenzene-4-pyridolidinobenzyl-piperacetonidyl-4-pyridolidinobenzyl-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzene-4-pyrrolidinobenzyl-4-pyrrolidinobenzyl-4 , 4-morpholinobenzylidene acetone, 4-diethylaminobenzylidene acetone, 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, 3-benzylidene-1,3-cyclohexanedione, 3- (4-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4- Dimethylamino-benzylidene) -1,3-cyclohexanedione, 3-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 3- (4-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 3- ( 4-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 3- (4-dimethylamino-benzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-B enzylidene-cyclopentanone, 2- (4-hydroxybenzylidene) - cyclopentanone, 2- (4-dimethylamino-benzylidene) -cyclopentanone, where 4-dimethylamino-benzylidene acetone, (1- (dimethylaminophenyl) -but-1-en-3-one) , 3,4-methylenedioxy-benzylidene acetone, 4-hydroxybenzylidene acetone and 3- (4-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione and their physiologically acceptable salts;
• - Unsaturated aldehydes with the formula (X) as described in the published patent application WO 98 47 473
  
  
  in the
  R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, halogen, a C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, aryl or C ₁ -C ₄ alkoxy C1 - C ₄ alkyl radical and
  x stands for the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ^{4 can} each form a 5- to 7-membered ring together with the rest of the molecule, if x is 1, and the corresponding mono-, bis- especially w-bis-alkoxyacetals, for example glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy - 2,4,6-heptatrienal and its derivatives and their physiologically tolerable salts.

• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Entwicklertyp, in Kombination mit wenigstens einem weiteren Oxidationsfarbstoffvorprodukt vom Entwicklertyp
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Entwicklertyp, in Kombination mit wenigstens einem weiteren Oxidationsfarbstoffvorprodukt vom Kupplertyp
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Entwicklertyp, in Kombination mit wenigstens einem weiteren direktziehenden Farbstoff
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Entwicklertyp, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von einem Derivat des Indols oder Indolins als Vorläufer des Melanins
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Entwicklertyp, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von Isatin oder einem seiner Derivate
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Entwicklertyp, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von als Farbstoff und/oder Farbstoffvorprodukt geeigneten Carbonylverbindungen
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Kupplertyp, in Kombination mit wenigstens einem weiteren Oxidationsfarbstoffvorprodukt vom Entwicklertyp
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Kupplertyp, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von einem Derivat des Indols oder Indolins als Vorläufer des Melanins
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Kupplertyp, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von Isatin oder einem seiner Derivate
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Oxidationsfarbstoffvorprodukt vom Kupplertyp, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von als Farbstoff und/oder Farbstoffvorprodukt geeigneten Carbonylverbindungen
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem direktziehenden Farbstoff, in Kombination mit wenigstens einem weiteren direktziehenden Farbstoff
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem direktziehenden Farbstoff, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von einem Derivat des Indols oder Indolins als Vorläufer des Melanins
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem direktziehenden Farbstoff, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von Isatin oder einem seiner Derivate
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem direktziehenden Farbstoff, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von als Farbstoff und/oder Farbstoffvorprodukt geeigneten Carbonylverbindungen
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Derivat des Indols oder Indolins als Vorläufer des Melanins, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von einem Derivat des Indols oder Indolins als Vorläufer des Melanins
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Derivat des Indols oder Indolins als Vorläufer des Melanins, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von Isatin oder einem seiner Derivate
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von einem Derivat des Indols oder Indolins als Vorläufer des Melanins, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von als Farbstoff und/oder Farbstoffvorprodukt geeigneten Carbonylverbindungen
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von Isatin oder einem seiner Derivate, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von Isatin oder einem seiner Derivate
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von Isatin oder einem seiner Derivate, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von als Farbstoff und/oder Farbstoffvorprodukt geeigneten Carbonylverbindungen
• - mindestens ein pflegender Hybridfarbstoff und/oder Hybridfarbstoffvorprodukt der Struktur (I) mit einer Gruppe F, abgeleitet von als Farbstoff und/oder Farbstoffvorprodukt geeigneten Carbonylverbindungen, in Kombination mit wenigstens einem Farbstoff, der sich ableitet von als Farbstoff und/oder Farbstoffvorprodukt geeigneten primären und/oder sekundären Amins und/oder CH-aciden Verbindungen.

In the context of these embodiments, the following embodiments can thus be preferred for variable care component P for the care-containing hybrid dyes and / or hybrid dye precursors of the formula (I):

• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the developer type, in combination with at least one other oxidation dye precursor of the developer type
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the developer type, in combination with at least one other oxidation dye precursor of the coupler type
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the developer type, in combination with at least one further direct dye
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the developer type, in combination with at least one dye which is derived from a derivative of indole or indoline as a precursor of melanin
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the developer type, in combination with at least one dye which is derived from isatin or one of its derivatives
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the developer type, in combination with at least one dye which is derived from carbonyl compounds suitable as a dye and / or dye precursor
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the coupler type, in combination with at least one other oxidation dye precursor of the developer type
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the coupler type, in combination with at least one dye which is derived from a derivative of indole or indoline as a precursor of melanin
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the coupler type, in combination with at least one dye which is derived from isatin or one of its derivatives
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from an oxidation dye precursor of the coupler type, in combination with at least one dye which is derived from carbonyl compounds suitable as a dye and / or dye precursor
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from a direct dye, in combination with at least one further direct dye
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from a direct dye, in combination with at least one dye derived from a derivative of indole or indoline as a precursor of melanin
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from a direct dye, in combination with at least one dye which is derived from isatin or one of its derivatives
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from a direct dye, in combination with at least one dye which is derived from carbonyl compounds suitable as a dye and / or dye precursor
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from a derivative of indole or indoline as a precursor of melanin, in combination with at least one dye which is derived from a derivative of indole or indoline as Precursor of melanin
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from a derivative of indole or indoline as a precursor of melanin, in combination with at least one dye which is derived from isatin or one of its derivatives
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from a derivative of indole or indoline as a precursor of melanin, in combination with at least one dye which is derived from suitable as a dye and / or dye precursor carbonyl
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from isatin or one of its derivatives, in combination with at least one dye which is derived from isatin or one of its derivatives
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from isatin or one of its derivatives, in combination with at least one dye which is derived from carbonyl compounds suitable as a dye and / or dye precursor
• - At least one caring hybrid dye and / or hybrid dye precursor of structure (I) with a group F, derived from carbonyl compounds suitable as dye and / or dye precursor, in combination with at least one dye which is derived from primary and suitable as dye and / or dye precursor / or secondary amine and / or CH-acidic compounds.

The agents according to the invention contain the further oxidation dye precursors of Coupler type, developer type oxidation dye precursors, derivatives of indole or Indoline as a precursor to melanin, direct dyes, and / or isatin and its Derivatives and / or suitable as a dye and / or dye precursor Carbonyl compounds usually in amounts of 0% by weight - 20% by weight, preferably 0.01% by weight to 10% by weight, based on the total colorant. amounts from 0.05% by weight to 5% by weight, in particular from 0.1% by weight to 3% by weight, are special prefers.

In the context of the embodiments mentioned, it is not necessary that the Oxidation dye precursors, substantive dyes or melanin precursors, isatin Dyes and / or suitable as a dye and / or dye precursor Carbonyl compounds each represent uniform compounds. Rather, in the colorants of the invention, due to the manufacturing process for individual dyes, contain minor components in minor amounts to the extent that these do not adversely affect the coloring result or from others Reasons, e.g. B. toxicological, must be excluded.

Regarding the usable in the colorants and tints according to the invention Dyes are further expressly referred to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), appeared as Volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in disk form from the Federal Association of German Industrial and trading company for pharmaceuticals, health products and Personal care products e. V., Mannheim, referred to.

Agents according to the invention, containing at least one nourishing hybrid dye and / or hybrid dye precursor of structure (I), contained according to a special Embodiment other than the mentioned caring hybrid dyes and / or Hybrid dye precursors no other dyes or dye precursors.

In a further preferred embodiment, the inventive Coloring agent and additional care components. As part of the present Invention hair care components are understood to mean those substances that have a have a demonstrably positive effect on the hair structure, so-called "cortical modifiers ".

Examples of preferred hair care components according to the invention as structure-improving agents are vitamins and their derivatives respectively Precursors. Panthenol and its are particularly preferred according to the invention physiologically acceptable derivatives. Such derivatives are in particular the esters and Panthenol ethers and cationically derivatized panthenols. Individual representatives are for example panthenol triacetate, panthenol monoethyl ether and the like Monoacetate and the cationic ones disclosed in WO 92/13829 A1 Panthenol. A panthenol derivative preferred according to the invention is also its Precursor pantolactone. Panthenol is preferred within this group.

Furthermore, polyvinylpyrrolidone (PVP) is also used for its fiber structure-improving Properties known and preferred according to the invention.

Other structure-improving compounds which are particularly effective according to the invention represent the aldehydes. Particularly preferred examples are formaldehyde and Formaldehyde-releasing compounds, such as methoxymethyl ester, Dimethylol (thio) urea derivatives, oxazolidine derivatives, N-hydroxymethylmaleinimide, Hexamethylenetetramine and its derivatives, hydantoin derivatives, pyridinium-substituted Dimethyl ether, imidazolidinyl urea derivatives, isothiazolinones, 2-bromo-2-nitropropanediol and 5-bromo-5-nitro-1,3-dioxane. Other particularly preferred aldehydes are Acetaldehyde, glyoxal, glyceraldehyde and glutardialdehyde.

Another suitable group of structure-improving agents are Plant extracts.

These extracts are usually produced by extracting the entire plant. In individual cases, however, it may also be preferred to use the extracts exclusively To produce flowers and / or leaves of the plant.

With regard to the plant extracts which can be used according to the invention, particular reference is made to the extracts pointed out in the on page 44 of the 3rd edition of the guide to Ingredient declaration of cosmetic products, published by the industry association Toiletries and detergents e. V. (IKW), Frankfurt, starting table are.

According to the invention, the extracts from oak bark, nettle, witch hazel, Hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe Vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosmann, Birch, Mallow, Cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, coltsfoot, Marshmallow, meristem, green tea, ginseng and ginger root preferred.

The extracts from oak bark, nettle, witch hazel, hops, Chamomile, burdock root, horsetail, linden flowers, almond, aloe vera, coconut, Mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, Rosmann, Birch, Cuckoo Flower, Quendel, Yarrow, Hauhechel, Meristem, green tea, Ginseng and ginger root.

The extracts from almond are particularly suitable for the agents according to the invention, Aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon and green tea.

As extracting agents for the production of the plant extracts mentioned, water, Alcohols and their mixtures can be used. Among the alcohols are included lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethenyl glycol and propylene glycol, both as the sole extractant and in Mix with water, preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

According to the invention, the plant extracts can be either pure or diluted Form are used. If they are used in diluted form, they contain usually about 2-80 wt .-% active substance and as a solvent that in their Extraction or extractant mixture used.

It may furthermore be preferred to use mixtures of the agents according to the invention use several, in particular from two, different plant extracts.

Also preferred according to the invention as structure-improving agents Honey extracts. These extracts are analogous to the plant extracts won and usually contain 1-10 wt .-%, in particular 3-5 wt .-%, Active substance. Water / propylene glycol mixtures can also be preferred here Extractant.

Other structure-improving active ingredients are protein hydrolyzates, in particular elastin, Collagen, keratin, milk protein, soy protein, almond protein and Wheat protein hydrolyzates, their condensation products with fatty acids as well as quaternized Protein. Heavily degraded keratin hydrolyzates are particularly preferred Molar masses in the range from 400 to 800. Furthermore, quaternized protein hydrolyzates, such as for example under the trade names Gluadin® WQ (INCI name: Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein) and Crotein® Q (INCI- Name: Hydroxypropyltrimonium Hydrolyzed Collagen) are sold, particularly preferred according to the invention.

In addition to the quaternized protein hydrolyzates, there are also quaternary polymers Structure-improving compounds preferred according to the invention. Particular the polymers which are preferred under the trade names Mirapol® A15 (INCI- Name: Polyquaternium-2), Onamer® M (INCI name: Polyquaternium-1) and Merquat® 100 (INCI name: Polyquaternium-6) are sold.

Active ingredients that improve fiber structure are also mono-, di- and oligosaccharides such as for example glucose, galactose, fructose, fructose, sucrose and lactose. Derivatives of these pentoses and hexoses, such as the corresponding ones, can also be used On and uronic acids (sugar acids), sugar alcohols, sugar amines, such as N- Glucosamine, N-glucamine, and glycosides can be used according to the invention. The According to the invention, sugar acids in free form, in the form of their salts, are preferred Calcium, magnesium and zinc salts, and used in the form of their esters or lactones become. Preferred sugar acids are gluconic acid, gluconic acid-γ-lactone, Lactobionic acid, glucuronic acid and its mono- or dilactones, the Pangamic acid, sugar acid, mannosugaric acid and their mono- respectively Dilactones as well as mucic acid and its mono- or dilactones. preferred Sugar alcohols are sorbitol, mannitol and dulcitol. Preferred glycosides are Methylglucoside. Glucose, N-glucosamine and gluconic acid are from this group particularly preferred.

Certain amino acids are also within the scope of the present invention active ingredients that improve hair structure. Examples are those in DE-195 22 569, to which amino acids serine are expressly referred to, Threonine and tyrosine. Furthermore, derivatives of serine, such as that Serine phosphate, preferred according to the invention. Other structure-improving amino acids represent lysine and arginine. Serine and arginine are particularly preferred active ingredients that improve fiber structure.

Certain acids, in particular, can also be used to improve the structure α-Hydroxycarboxylic acids, and their salts are used. Preferred according to the invention structure-improving acids are lactic acid, malic acid, citric acid, tartaric acid, Glyceric acid and maleic acid. Lactic acid is particularly preferred. Continue to improve special phosphonic acids and their salts the structure of keratin fibers. Preferred phosphonic acids according to the invention are the n-octylphosphonic acid and the n- Decylphosphonic.

Lipid-soluble ester alcohols or ester polyols are also used to improve their structure Effect known. They are to be regarded as lipid-soluble if they contain 5% by weight Dissolve products clearly in cetyl alcohol at 80 ° C.

The ester alcohols or ester polyols suitable according to the invention are obtainable from Implementation of an epoxy fatty acid ester with water or mono- or polyhydric alcohols with 1-10 C atoms opening the epoxy ring and forming a vicinal Dihydroxyethyl or hydroxyalkoxyethyl group. The epoxy fatty acid ester can also an epoxidation product from a technical fatty acid ester with proportions saturated fat. However, the epoxy oxygen content should be at least 3% by weight, preferably 5-10% by weight.

The epoxy fatty acid esters are either epoxidized fatty acid esters Alcohols, e.g. B. epoxidized oleic acid methyl ester, linoleic acid methyl ester, Ricinoleic acid methyl ester or epoxidized fatty acid esters of polyhydric alcohols, e.g. B. Glycerol monooleate or propylene glycol monooleate or epoxidized fatty acid triglycerides, z. B. oleic acid triglyceride or unsaturated oils such. B. olive oil, soybean oil, sunflower oil, Linseed oil, rape oil.

Unsaturated fatty acid methyl ester epoxides are of particular technical interest from unsaturated vegetable fatty acids. As the ester polyol, the reaction product is one Vegetable oil fatty acid methyl ester epoxidate with a polyol with 2-6 C atoms and 2-6 Hydroxyl groups are particularly preferred. As polyols, z. B. ethylene glycol, 1,2- Propylene glycol, 1,3-propylene glycol, butanediol, pentanediol, hexanediol, glycerin, Trimethylolpropane, pentaerythritol, sorbitol or diglycerol can be included.

It is particularly well suited for the hair treatment compositions according to the invention Ester polyol with the reaction product of a vegetable fatty acid methyl ester epoxidate Trimethylpropane and with a hydroxyl number of 350-450. Such a product based of soybean oil fatty acid methyl ester epoxy and trimethylolpropane is among the Trade name Sovermol®760 available.

Vitamin B ₃ can also be used as a structure-improving agent. The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. The nicotinamide is preferred according to the invention.

Vitamin H is also a structure-improving agent in the sense of the present Invention can be used. The compound (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] -imidazole-4-valeric acid, but for which meanwhile the trivial name has prevailed biotin.

Structure-improving active ingredients which are particularly preferred according to the invention are selected from protein hydrolyzates, in particular with M <1000, from milk protein, wheat (such as Gluadin® WQ) and collagen hydrolyzate (such as Crotein® Q), Mirapol® A15 (Polyquaternium 2), glucose, fructose, serine, serine phosphate, lactic acid, tartaric acid, Glyceric acid, nicotinamide, pantolactone, panthenol, vitamin B6 and biotin.

The agents according to the invention preferably contain additional care components in amounts from 0 to 20% by weight, more preferably 0.1 to 10% by weight, in particular 1 to 4% by weight, based on the total mean.

According to a further preferred variant, the agents according to the invention also contain at least one nourishing hybrid dye and / or hybrid dye precursor Structure (I) in which F is derived from indoline or which are further contained in indole / indoline at least one amino acid or an oligopeptide.

Amino acids in the sense of the invention are substances which have at least one amino group and at least one -COOH or -SO ₃ H group.

Preferred amino acids are amino carboxylic acids, especially α-amino carboxylic acids and ω-aminocarboxylic acids. Among the α-aminocarboxylic acids are arginine, Lysine, ornithine, serine and histidine are particularly preferred.

The amino acids of the agents according to the invention can preferably be in free form be added. It is also possible to use the amino acids in salt form. preferred Salts are then the compounds with hydrohalic acids, especially those Hydrochloride and the hydrobromide.

Very particularly preferred amino acids are lysine and especially arginine, used in particular in free form, but also as hydrochloride.

Furthermore, the amino acids can also be in the form of oligopeptides and Protein hydrolyzates are used if it is ensured that the required amounts of Compounds which correspond to the definition of the amino acids according to the invention therein are included. In this context, the disclosure of DE-OS 22 15 303 referred to, to which express reference is made.

Of course, the invention also includes such means, the two and more Contain amino acids or oligopeptides. Combinations of arginine with are preferred another amino acid or an oligopeptide.

The agents according to the invention preferably contain the amino acid or the oligopeptide in amounts of 0 to 20% by weight, more preferably 0.1 to 10% by weight, in particular 1 to 4 % By weight, based on the total average.

Colorants, especially if the coloration is oxidative, be it with atmospheric oxygen or other oxidizing agents, such as hydrogen peroxide, usually become weak acidic to alkaline, d. H. adjusted to pH values in the range of about 5 to 11. To for this purpose, the colorants contain alkalizing agents, usually alkali or Alkaline earth metal hydroxides, ammonia or organic amines.

Because there is an undesirable cleavage of the acidic or neutral pH nourishing hybrid dyes and / or hybrid dye precursors according to the invention in their individual components can come in a particularly preferred Embodiment of the agents according to the invention an alkaline pH of 7 to 10 set.

According to a special embodiment of the present invention, the Amino acid or the oligopeptide not only to intensify the coloration but also also takes over, at least in part, the function of the alkalizing agent. As part of In this embodiment, such amino acids and oligopeptides are preferred used, whose 2.5 wt .-% solutions in water have a pH of 9 and greater exhibit. Such amino acids are the preferred arginine compounds and lysine. In the context of this embodiment, the further alkalizing agent preferably selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol and triethanolamine as well as alkali and Alkaline earth metal hydroxides is formed. In particular monoethanolamine, triethanolamine and 2- Amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are within the scope of these Group preferred. Also the use of ω-amino acids such as ω-aminocaproic acid is preferred as an alkalizing agent in the context of this embodiment.

Particularly advantageous properties have been found in agents in which the Amino acid or the oligopeptide and the further alkalizing agent in a ratio of 1: 5 to 5: 1. Ratios of 1: 2 to 2: 1 have been found to be particularly suitable proved.

To produce the colorants according to the invention, those mentioned above are used mandatory and optional components in a suitable, preferably water-containing, Carrier incorporated. Such carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming solutions, e.g. B. shampoos, aerosols or other preparations, which are suitable for use on the hair. These wording forms will with the alkalizing agents or suitable acids already mentioned above, such as especially phosphoric acid and HCl as well as edible acids such as citric acid, tartaric acid, Lactic acid and acetic acid, preferably to a pH of 5 to 11, in particular 7 up to 10.

Furthermore, the colorants according to the invention can all be in such preparations known active ingredients, additives and auxiliary substances. In many cases, the colorants contain at least one surfactant, in principle both anionic and zwitterionic, Ampholytic, nonionic and cationic surfactants are suitable. In many cases it has but proved to be advantageous, the surfactants from anionic, zwitterionic or select nonionic surfactants. Anionic surfactants can be very special be preferred. The surfactants are used in amounts of 0-40% by weight, preferably 0.5-30 % By weight, particularly preferably 1-15% by weight, based on the total colorant, used.

Suitable anionic surfactants in preparations according to the invention are all suitable for Use of anionic surfactants suitable for the human body.

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

These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ether, amide and hydroxyl groups and generally also ester groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Monosulfonic acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• linear alkanesulfonates with 12 to 18 carbon atoms,
• linear alpha olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (-CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

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

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) -D group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylamino-propyl-dimethylammonium glycinate, and 2 -Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacyl-aminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₁₈ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkylimino dipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acyl amino ethyl aminopropionate and C _12-18 acyl sarcosine.

• - 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, deren ethoxylierte Analoga und deren Ester z. B. mit Weinsäure und Citronensäure,
• - Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• - Anlagerungsprodukte von Ethylenoxid an Sorbitanfettsäureester,
• - Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide.

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

• Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ alkyl mono- and oligoglycosides, their ethoxylated analogs and their esters z. B. with tartaric acid and citric acid,
• - adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,
• Addition products of ethylene oxide onto sorbitan fatty acid esters,
• - Adducts of ethylene oxide with fatty acid alkanolamides.

Examples of those which can be used in the hair treatment compositions according to the invention Cationic surfactants are especially quaternary ammonium compounds. Are preferred Ammonium halides such as alkyltrimethylammonium chlorides, Dialkyldi-methylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and Tricetylmethylammonium chloride. Provide further cationic surfactants that can be used according to the invention the quaternized protein hydrolyzates.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxyl-amino-modified silicone, also known as amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines like the one under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect especially due to its good biodegradability.

Quaternary ester compounds, so-called "Esterquats", such as those sold under the Stepantex® trademark Methyl-hydroxyalkyl-dialkoyloxyalkyl-ammonium methosulfates and the corresponding products, which are commercially available under the trademark Dehyquart®.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided represents the commercial product Glucquat®100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 hydroxypropyl dimonium chloride ".

The compounds with alkyl groups used as surfactants can in each case be act uniform substances. However, it is usually preferred in manufacturing these substances from natural vegetable or animal raw materials, so that one Mixtures of substances with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Fatty alcohols or derivatives of these adducts can represent both Products with a "normal" homolog distribution as well as those with a narrow Homolog distribution can be used. Under "normal" homolog distribution understood mixtures of homologues that are used in the implementation of Fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution can be preferred.

According to the invention, the use of anionic surfactants in combination with zwitterionic surfactants may be particularly preferred.

Also preferred according to the invention are those agents which additionally contain a cationic agent Polymer included.

The permanent cationic polymers are among the cationic polymers prefers. According to the invention, such polymers are termed “permanently cationic” if which have a cationic group regardless of the pH of the agent. These are in usually polymers that have a quaternary nitrogen atom, for example in the form of a Ammonium group.

• - quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR®400 sind bevorzugte quaternierte Cellulose-Derivate,
• - Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning® 929 Emulsion (enthaltend ein hydroxyl-aminomodifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydimethylsiloxane, Quaternium-80),
• - Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia®Guar und Jaguar® vertriebenen Produkte,
• - Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere,
• - Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quatemierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat®734 und Gafquat®755 im Handel erhältlich,
• - Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat® FC 370, FC 550, FC 905 und HM 552 angeboten werden,
• - quaternierter Polyvinylalkohol,
• - sowie die unter den Bezeichnungen
• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 und
• - Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives,
• Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxyl-amino-modified silicone, which is also referred to as amodimethicone), SM- 2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• - Cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia®Guar and Jaguar®,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755,
• Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as are offered under the names Luviquat® FC 370, FC 550, FC 905 and HM 552,
• - quaternized polyvinyl alcohol,
• - as well as under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Can also be used as cationic polymers under the Designations Polyquaternium-24 (commercial product e.g. Quatrisoft® LM 200), Polyquaternium- 32, Polyquaternium-35 and Polyquaternium-37 (commercial products e.g. Salcare® SC 92 and Salcare®SC 95) known polymers. The can also be used according to the invention Copolymers of vinyl pyrrolidone, as are commercially available as copolymer 845 (Manufacturer: ISP), Gaffix® VC 713 (Manufacturer: ISP), Gafquat®ASCP 1011, Gafquat®HS 110, Luviquat®8155 and Luviquat® MS 370 are available.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives, polymeric dimethyldiallylammonium salts, polyquaternium-27 and their copolymers as well as polymers of the type polyquaternium-2. Cationic cellulose derivatives, in particular the commercial product Polymer®JR 400, and polymers of the type Polyquaternium-2, in particular the commercial product Mirapol®A-15 are very particularly preferred cationic polymers.

The cationic polymers are preferred in amounts in the agents according to the invention from 0 to 10% by weight, in particular 0.05 to 5% by weight, based on the total Preparation included.

In many cases, amphopolymers can also be used as an alternative to the cationic polymers. Ampho-polymers include amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^- or -SO ₃ ^- groups, and summarize those polymers which contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer that can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acid (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acid (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the prior art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, and the commercial product Merquat®280 can also be used according to the invention.

The agents according to the invention likewise preferably contain at least one non-ionic or anionic polymer with thickening properties. Preferred are optionally crosslinked, polyacrylic acids, cellulose derivatives, e.g. B. methyl cellulose, Hydroxyalkyl cellulose and carboxymethyl cellulose, and xanthan gum.

According to the invention, the polymers are used in amounts of 0-30% by weight, preferably 0.1-25 % By weight, particularly preferably 0.5-10% by weight, based on the total colorant, used.

• - nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und VinylpyrrolidonlVinylacetat-Copolymere und Polysiloxane,
• - anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere,
• - Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Gummi arabicum, Karaya- Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• - haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline, sowie Silikonöle,
• - Parfümöle, Dimethylisosorbid und Cyclodextrine,
• - Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin, Diethylenglykol, Ethoxybutanol und Butoxyethanol sowie Benzylalkohol,
• - Antischuppenwirkstoffe wie Piroctone Olamine und Zink Omadine,
• - weitere Substanzen zur Einstellung des pH-Wertes, wie beispielsweise α- und β- Hydroxycarbonsäuren,
• - Wirkstoffe wie Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze und Vitamine,
• - Cholesterin,
• - Lichtschutzmittel,
• - Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• - Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsäureester,
• - Fettsäurealkanolamide,
• - Komplexbildner wie EDTA, NTA und Phosphonsäuren,
• - Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• - Trübungsmittel wie Latex, Perlglanzmittel wie Ethylenglykolmono- und -distearat,
• - Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• - Antioxidantien.

Other active ingredients, auxiliaries and additives are, for example

• nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidonl / vinyl acetate copolymers and polysiloxanes,
• - anionic polymers such as 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-butylacrylamide terpolymers
• - Thickeners such as agar agar, guar gum, alginates, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,
• hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, ethoxybutanol and butoxyethanol and benzyl alcohol,
• - anti-dandruff agents such as Piroctone Olamine and Zink Omadine,
• further substances for adjusting the pH, such as, for example, α- and β-hydroxycarboxylic acids,
• Active substances such as pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts and vitamins,
• - cholesterol,
• - light stabilizers,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as whale, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, pearlescent agents such as ethylene glycol mono- and distearate,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

The components of the water-containing carrier are used to manufacture the Colorants according to the invention used in amounts customary for this purpose; z. B. be Emulsifier in concentrations of 0 to 40% by weight, preferably 0.5 to 30% by weight and Thickeners in concentrations of 0 to 30% by weight, preferably 0.1 to 20% by weight of the entire colorant used.

Regarding the other components of the colorants according to the invention, too expressly to the monographs known to the person skilled in the art, e.g. B. Umbach, cosmetics, 2. Edition, Georg Thieme Verlag, Stuttgart New York, 1995, and Kh. Schrader, Fundamentals and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, directed.

All known methods can be used to form the color on the keratin fiber be applied.

According to a preferred embodiment, the coloring is carried out with Atmospheric oxygen as the only oxidant. This embodiment is particularly then preferred if the group F of the caring hybrid dye differs from a precursor derives from melanin or air-oxidizable developer and coupler components, or that Medium precursor of melanin and / or air-oxidable dye precursors from the coupler or developer type. According to the invention, such as air-oxidizable compounds are To understand compounds or dye precursors in which the oxidative training the final coloring with the help of atmospheric oxygen alone without using conventional ones chemical oxidizing agents can take place. Triaminobenzene derivatives are examples of such air-oxidizable compounds.

In certain cases, where the group F of the caring hybrid dye differs from derives from a precursor of melanin or developer and coupler components, or the agent precursor of melanin and / or dye precursors from the coupler or Contains developer type, but the use of a chemical oxidizing agent be desired. This also applies if, in addition to the coloring, there is an auto-brightness effect human hair is desired. Then come in particular as oxidizing agents Hydrogen peroxide or its adducts with urea, melamine or Sodium borate in question.

The preparation of the oxidizing agent is expediently immediately before Coloring the hair mixed with the preparation with the dye precursors. That included The resulting ready-to-use dye preparation should preferably have a pH in the range have from 5 to 11. The use of the colorants in one is particularly preferred weakly alkaline environment. Application temperatures can range between 15 and 40 ° C, preferably at the temperature of the scalp. After a The colorant becomes an exposure time of approx. 5 to 45, in particular 15 to 30, minutes removed by rinsing from the hair to be dyed. The washing up with a Shampoo is not required if a carrier with a high tenside content, e.g. B. a coloring shampoo used has been.

Especially with hair that is difficult to dye, the preparation can be used with the Dye precursors without prior mixing with the oxidation component on the hair be applied. After an exposure time of 20 to 30 minutes, optionally after an intermediate rinse - the oxidation component applied. After a further exposure time of 10 to 20 minutes, rinse and post-shampooed if desired. In this embodiment, according to a first Variant in which the previous application of the dye precursors is better Penetration in the hair is said to bring the appropriate agent to a pH of about 4 to 10, in particular 7 to 10, set. According to a second variant air oxidation is initially sought, the applied agent preferably one pH of 7 to 10. During the subsequent accelerated post-oxidation can the use of acidified peroxodisulfate solutions as Oxidizing agents may be preferred.

According to a special embodiment of this method, the final staining by applying the agent several times and each subsequent air oxidation. The respective application of the agent is preferably carried out in Intervals that range from about a day to about two weeks. This allows very specific nuances are obtained.

Regardless of which of the above-mentioned methods is chosen for using the agent according to the invention, the formation of the color can be supported and increased by adding certain metal ions to the agent. Such metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

It is also possible according to the invention to carry out the oxidation with the aid of enzymes perform. The enzymes (enzyme class 1: oxidoreductases) can remove electrons transfer suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase and laccase are preferred, but also glucose oxidase and uricase or pyruvate oxidase. Furthermore, the enzymes can be lower to enhance the effect Amounts of existing oxidizing agents are used. An example of such enzymatic process represents the procedure, the effect of small amounts (e.g. 1% and less, based on the total agent) hydrogen peroxide by peroxidases strengthen.

Another object of the invention is the use of the caring Hybrid dyes and / or hybrid dye precursors of structure (I) or a mixture of these hybrid dyes and / or hybrid dye precursors containing agents for Dyeing keratin fibers, especially human hair.

Furthermore, it has been shown that the caring hybrid dyes according to the invention and / or hybrid dye precursors of structure (I) or a mixture thereof Agents containing hybrid dyes and / or hybrid dye precursors are also suitable excellent for coloring, especially for tanning, the human skin. Another object of the invention is therefore the use of the caring Hybrid dyes and / or hybrid dye precursors of structure (I) or a Mixture of these hybrid dyes and / or containing hybrid dye precursors Preparations for coloring human skin.

Another object of the invention are those in the colorants according to the invention contained nourishing hybrid dyes and / or hybrid dye precursors of the structure (I) for dyeing keratin fibers, wherein the dye component F is selected from Derivatives of indole or indoline as precursors of melanin, isatin and derivatives of isatin or is derived from suitable dyes and / or dye precursors Carbonyl compounds.

Another object of the invention are those in the colorants according to the invention contained nourishing hybrid dyes and / or hybrid dye precursors of the structure (I) for dyeing keratin fibers, the care component P being derived from a Compound selected from the group comprising sugar, in particular glucose, Mannose, galactose and / or allose, polyols, vitamins, especially panthenol and Derivatives thereof, peptides, hydroxy acids and polyhydroxy acids as well as physiologically compatible salts or phosphoric acid derivatives of the aforementioned compounds.

Caring agents are particularly preferred in the context of the present invention Hybrid dyes and / or hybrid dye precursors of structure (I) selected are from the group comprising 2- (2,4-dinitrophenylamino) -2-hydroxymethylpropane-1,3- diol, 2- (2,4-diaminophenylamino) -2-hydroxymethylpropane-1,3-diol hydrochloride, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (2,4-dinitrophenylamino) ethyl) amide, 2,3,4,5,6- Pentahydroxyhexanoic acid- (2- (4-acetylamino-2-nitrophenylamino) ethyl) amide, 2,3,4,5,6- Pentahydroxyhexanoic acid- (2- (5-nitropyridin-2-ylamino) ethyl) amide, 2,3,4,5,6- Pentahydroxyhexanoic acid- (2- (4-amino-2-nitrophenylamino) ethyl) amide, N- (4-allylamino-3- nitrophenyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranosylamine, N- (3-nitro-4-pyrrolidin-1- yl-phenyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranosylamine, N- (4-allylamino-3- nitrophenyl) -α, β-D-glucopyranosylamine, N- (4-allylamino-3-nitrophenyl) -α, β- (4-β-D- galactopyranosyl) -D-glucopyranosylamine, N- (4-allylamino-3-nitrophenyl) -α, β-D- galactopyranosylamine, 2- (6-amino-4-carboxy-2-nitrophenylamino) -2-deoxy-α, β-D- glucopyranose, 2- (4-cyano-2,6-dinitrophenylamino) -2-deoxy-α, β-D-glucopyranose, 2- (4- Carboxy-2,6-dinitrophenylamino) -2-deoxy-α, β-D-glucopyranose, N- (4-allylamino-3 - nitrophenyl) -2-acetamido-2-deoxy-α, β-D-glucopyranosylamine, 1-O- (4-methyl-2- nitrophenylaminoethyl) -α, β-D-glucopyranose and / or N- (5-aminopyrid-2-yl) -α, β-D- glucopyranosyl amine hydrochloride.

Another object of the invention is the use of care Hybrid dyes and / or hybrid dye precursors of structure (I) or one Mixture of these hybrid dyes and / or hybrid dye precursors for dyeing keratin fibers, especially human hair.

Furthermore, it has been shown that the caring hybrid dyes according to the invention and / or hybrid dye precursors are also excellent for staining, in particular suitable for tanning, human skin. Another object of the invention is hence the use of the caring hybrid dyes and / or Hybrid dye precursors of structure (I) or a mixture of these hybrid dyes and / or hybrid dye precursors for coloring human skin.

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

Examples I. Nourishing hybrid dyes which can be used in the colorants according to the invention and / or hybrid dye precursors 1. Compounds based on 2-deoxy sugars 1.1. 2- (4-carboxy-2,6-dinitrophenylamino) -2-deoxy-α, β-D-glucopyranose Hybrid dye 1

P derived from glucose

F derived from a direct puller (4-amino-3,5-dinitrobenzoic acid)

S stands for an N-structural element, which is the common component of groups P and F. is

synthesis

A light yellow suspension of 2.7 g (11.0 mmol) of 4-chloro-3,5-dinitrobenzoic acid in 50 ml of an acetone: water mixture (1: 4) was added at room temperature. 4.3 ml (31.0 mmol) of triethylamine were carefully added dropwise. 2.0 g (9.3 mmol) of glucosamine hydrochloride were slowly added to this solution. After stirring for 21 h at room temperature. the acetone was distilled off under vacuum. The remaining reaction mixture was diluted with 20 ml of water and extracted seven times with 30 ml of ethyl acetate. The aqueous phase was slowly acidified with HCl at 0 ° C. The mixture was then extracted several times with tert-butyl methyl ether, the combined organic phases were dried over sodium sulfate and the solvent was distilled off under vacuum after drying. The remaining residue was dried at 40 ° C overnight. Yellow powder with mp 192-199 ° C (dec.)
Yield: 52% 1.2. 2- (6-amino-4-carboxy-2-nitrophenylamino) -2-deoxy-α, β-D-glucopyranose hybrid dye 2

P derived from glucose
F derived from a direct puller (4,5-diamino-3-nitrobenzoic acid)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

4.8 g (12.33 mmol) of 2- (4-carboxy-2,6-dinitrophenylamino) -2-deoxy-α, β-D-glucopyranose (hybrid dye 2) was dissolved in 240 ml of methanol in a hydrogenation duck. Then 0.11 g (141.0 mmol) of Pd (5% on C) were introduced under nitrogen and hydrogenated at 1013 mbar. After the sufficient amount of H _{2 had been} taken up, the mixture was filtered off through Primisil and the filtrate was distilled off at 40 ° C. under vacuum. black-brown powder
¹ H-NMR (400 MHz, DMSO-d ₆ ) δ (ppm): β-anomer: 8.2 (d, 1H, H _arom. ); 7.8 (d, 1H, H _arom. ); 4.7 (d, 1H, HC (anomer)); 3.0-3.8 (m, 6H, CH and CH ₂ ); α-anomer: 8.0 (d, 1H, H _arom. ); 7.3 (d, 1H, H _arom. ); 5.1 (d, 1H, HC (anomer)); 3.0-3.8 (m, 6H, CH and CH ₂ ); Anomer ratio α: β; 3: 1)
Yield: 65% 1.3. 2- (4-cyano-2,6-dinitrophenylamino) -2-deoxy-α, β-D-glucopyranose hybrid dye 3

P derived from glucose
F derived from a direct puller (4-amino-3,5-dinitrobenzonitrile)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

To a mixture of 3.6 g (15.8 mmol) of 4-chloro-3,5-dinitrobenzonitrile and 2.9 g (13.4 mmol) of glucosamine hydrochloride in 95 ml of an acetone: water mixture (1: 2.2) were at room temp. 4.0 ml (29.0 mmol) of triethylamine were carefully added dropwise, a dark red solution being obtained. After stirring for 20 h at room temperature. the acetone was distilled off under vacuum. The remaining reaction mixture was cooled to 4 ° C. overnight and the resulting precipitate was then filtered off and dried in vacuo. The mixture was then recrystallized from ethanol / hexane and the solid obtained was dried in vacuo. Yellow crystals with mp. 184-188 ° C.
Yield: 37% 2. Compounds based on O-glycosidically bound sugars 2.1. 1-O- (4-methyl-2-nitrophenylaminoethyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranose hybrid dye 4

P derived from tetra-O-acetylglucose
F derived from a direct puller (4-methyl-2-nitroaniline)
S stands for an ethylene group

synthesis

20.00 g (51.24 mmol) of β-D-glucose pentaacetate and 12.00 g (61.16 mmol) N- (2-hydroxyethyl) -2-nitrotoluidine in 100 ml of absolute dichloromethane.

After both components had dissolved with stirring, 33 ml of boron trifluoride etherate were slowly added dropwise. The reaction solution was then refluxed for 7 hours. The solution, cooled to room temperature, was carefully added to 200 ml of ice water. The organic phase was separated from the two-phase mixture and washed once with 20 ml of a saturated sodium hydrogen carbonate solution and then three times with 50 ml of water each. The mixture was then dried over sodium sulfate and the solvent was distilled off in vacuo. The oil initially obtained was crystallized by adding methanol. The precipitate obtained was filtered off, washed with methanol and dried in vacuo. Yellow needles with mp. 141-143 ° C.
Yield: 45%. 2.2. 1-O- (4-methyl-2-nitrophenylaminoethyl) -α, β-D-glucopyranose hybrid dye 5

P derived from glucose
F derived from a direct puller (4-methyl-2-nitroaniline)
S stands for an ethylene group

synthesis

4.4 g (8.36 mmol) of 1-O- (4-methyl-2-nitrophenylaminoethyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranose (hybrid dye 4) were added under nitrogen suspended in 220 ml of dry methanol. The mixture was then stirred at room temperature. 0.2 ml (1.08 mmol) sodium methylate solution (30% in methanol) was added dropwise. After 2 h the solution was concentrated in vacuo to 35% of the original volume at 35 ° C. It was then neutralized before the reaction mixture was further concentrated in vacuo. The residue was dried at 45 ° C in a vacuum. Orange-red powder with mp. 133-140 ° C.
Yield 98%. 3. Compounds based on N-glycosidically bound sugars 3.1. N- (4-Allylamino-3-nitrophenyl) -α, β-D-glucopyranosylamine hybrid dye 6

P derived from glucose
F derived from a direct puller (N- (1-allyl) -2-nitro-1,4-phenylenediamine)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

8.0 g (41.4 mmol) of N-1-allyl-2-nitro-1,4-phenylenediamine were dissolved in 127 ml of ethanol under nitrogen. Then an equimolar amount of the D (+) - glucose dissolved in 30 ml of water was added to the resulting red solution. By adding a few drops of conc. The reaction was started with acetic acid and the reaction mixture was stirred at room temperature for 92 h. The solvent was then distilled off in vacuo and the remaining residue was mixed with tert-butyl methyl ether and stirred for a further 24 h. The remaining residue was then suctioned off and boiled up several times with 100 ml of dichloromethane and then with 100 ml of hexane each time and suctioned off while hot. It was then washed again with 80 ml of hot dichloromethane. The remaining solid was isolated on a glass suction filter and dried in vacuo. Black-red powder with mp. 128-130 ° C.
Yield: 91% 3.2. N- (5-aminopyrid-2-yl) -α, β-D-glucopyranosylamine hydrochloride hybrid dye 7

P derived from glucose
F derived from a developer (2,5-diaminopyridine)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis Level I N- (5-nitropyrid-2-yl) -α, β-D-glucopyranosyl amine

2.8 g (20.13 mmol) of 2-amino-5-nitropyridine were dissolved in 15 ml of ethanol and added to a suspension of an equimolar amount of anhydrous glucose in 20 ml of ethanol. The reaction mixture was heated to boiling under reflux for 72 h, then cooled to room temperature and the resulting solid was filtered off with suction and washed with plenty of cold ethanol. Beige-brownish solid with a melting point of 178-180 ° C.
Yield: 76%

Stage II N- (5-aminopyrid-2-yl) -α, β-D-glucopyranosyl amine

2.00 g (6.78 mmol) of product from stage I were placed in 25 ml of isopropanol / water 1: 1, 0.2 g of Pd / C (10%) was added and hydrogen was added. The hydrogenation takes place at room temperature. After two hours, the catalyst was suctioned off through kieselguhr, the solution was acidified with 1N hydrochloric acid solution and evaporated in vacuo. The residue was taken up in water and freeze-dried.
Beige-pink lyophilisate, RF = 0.40 (isopropanol: water, 9: 1)
Yield: 93% 3.3. N- (4-Allylamino-3-nitrophenyl) -2-acetamido-2-deoxy-α, β-D-glucopyranosylamine hybrid dye 8

P derived from 2-acetamido-2-deoxyglucose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structural element, which is the common component of groups P and F.

synthesis

3.4 g (17.6 mmol) of N-1-allyl-2-nitro-1,4-phenylenediamine were dissolved in 50 ml of dry methanol under nitrogen. Subsequently, first 2.0 g (9.0 mmol) of N-acetyl-D-glucosamine, then 0.1 g (2.0 mmol) of ammonium chloride were added to the resulting red solution and the mixture was stirred under reflux for 12 h. The reaction mixture was then brought to room temperature. cooled, the resulting precipitate filtered off, washed with 25 ml of methanol and then dried in vacuo. Red needles with mp. 184-187 ° C.
Yield: 59% 3.4. N- (4-Allylamino-3-nitrophenyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranosylamine hybrid dye 9

P derived from tetra-O-acetylglucose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

To 4.0 g (21.0 mmol) of N-1-allyl-2-nitro-1,4-phenylenediamine in 45 ml of chloroform were added at room temperature. added 3.0 g (30.0 mmol) of triethylamine under nitrogen. A solution of 8.6 g (21.0 mmol) of acetobromglucose in 30 ml of chloroform was added dropwise to this reaction mixture, and the reaction mixture was then kept under reflux for 10 h. After cooling, the mixture was filtered off, washed with chloroform and the filtered solution was freed from the solvent in vacuo. The resulting red oil was recrystallized from about 50 ml of acetone, whereby a red precipitate was obtained, which in vacuo at room temperature. was dried. Red powder with mp 195-198 ° C.
Yield: 31% 3.5. N- (3-nitro-4-pyrrolidin-1-yl-phenyl) -2,3,4,6-O-tetraacetyl-α, β-D-glucopyranosylamine hybrid dye 10

P derived from tetra-O-acetylglucose
F derived from a direct puller (3-nitro-4-pyrrolidin-1-ylanilin)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

To a solution of 4.0 g (19.3 mmol) of 3-nitro-4-pyrrolidinylphenylamine in 30 ml of chloroform was first added 2.7 g (27.0 mmol) of triethylamine under nitrogen, then a solution of 7.9 g (19.3 mmol) of acetobromglucose in 25 ml of chloroform was added dropwise. The reaction mixture was heated to boiling under reflux for 10 h. After cooling, the mixture was filtered and the filtered solution was freed from the solvent in vacuo. The resulting oil was slurried in ethanol and placed on ice. The resulting precipitate was filtered off and dried in vacuo. Dark red powder with mp. 164-167 ° C
Yield: 28% 3.6. N- (4-Allylamino-3-nitrophenyl) -α, β-D-galactopyranosylamine hybrid dye 11

P derived from galactose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

7.0 g (36.2 mmol) of N-1-allyl-2-nitro-1,4-phenylenediamine were dissolved in 115 ml of ethanol under nitrogen. Then an equimolar amount of the D (+) - galactose dissolved in 25 ml of water was added to the resulting red solution. By adding a few drops of conc. The reaction was started with acetic acid and the reaction mixture was stirred for 94 h at room temperature. The solvent was then distilled off in vacuo and the remaining residue was slurried with 190 ml of tert-butyl methyl ether and stirred at RT for 19 h. The residue was filtered off and boiled several times in 85 ml of dichloromethane and several times in 86 ml of hexane each time and isolated over a glass suction filter and dried in vacuo. Red needles with mp. 133-136 ° C.
Yield: 81% 3.7. N- (4-hydroxyphenyl) -α, β-D-galactopyranosylamine hybrid dye 12

P derived from galactose
F derived from a developer (4-aminophenol)
S stands for an N-structural element, which is the common component of groups P and F.

synthesis

4.4 g (40.0 mmol) of 4-aminophenol and 6.13 g (34.0 mmol) of D (+) - galactose were refluxed for 10 hours with the addition of a few granules of zinc chloride and 1 ml of water. The cooled solution was concentrated until a precipitate formed, which was filtered off and then recrystallized from 30 ml of methanol / water (1: 1) and freeze-dried. Brown powder with mp 148-151 ° C.
Yield: 6% 3.8. N- (4-Allylamino-3-nitrophenyl) -α, β- (4-β-D-galactopyranosyl) -D-glucopyranosylamine hybrid dye 13

P derived from lactose
F derived from a direct puller (N-1-allyl-2-nitro-1,4-phenylenediamine)
S stands for an N-structural element, which is the common component of groups P and F.

synthesis

5.5 g (28.5 mmol) of N-1-allyl-2-nitro-1,4-phenylenediamine were dissolved in 90 ml of ethanol under nitrogen. Then an equimolar amount of the D-lactose dissolved in 45 ml of water was added to the resulting red solution. By adding a few drops of conc. The reaction was started with acetic acid and the reaction mixture was stirred for 118 h at room temperature. The suspension was filtered off and washed several times with 80 ml of tert-butyl methyl ether. The residue was then boiled up several times in 45 ml of dichloromethane and several times in hexane and suction filtered. The remaining solid was dried in vacuo. Red solid with mp 150-160 ° C (dec.).
Yield: 61%. 4. Compounds based on polyols 4.1. 2- (2,4-dinitrophenylamino) -2-hydroxymethylpropane-1,3-diol hybrid dye 14

P derived from 2-hydroxymethylpropane-1,3-diol
F derived from a direct puller (2,4-dinitroaniline)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

15 g (80 mmol) 2,4-dinitrofluorobenzene were at room temperature. submitted with nitrogen and stirring in about 60 ml of DMSO. 8.1 g (96 mmol) of NaHCO ₃ were first added to this mixture, then 9.76 g (80 mmol) of (trishydroxymethyl) methylamine were added rapidly in portions. The reaction mixture was then slowly heated to 40 ° C., at this temperature for about 3 minutes. held and after cooling for 1 h at room temp. touched. The mixture was then heated to 60 ° C. for about 30 minutes, cooled and the reaction mixture was poured onto ice. The resulting yellow precipitate was filtered off, slurried in 350 ml of water and warmed to about 85 to 90 ° C, then filtered hot. The resulting precipitate was filtered off and dried at 50 ° C in a vacuum. Yellow orange needles
Yield: 53% 4.2. 2- (2,4-diaminophenylamino) -2-hydroxymethylpropane-1,3-diol hydrochloride hybrid dye 15

P derived from 2-hydroxymethylpropane-1,3-diol
F derived from a developer (1,2,4-phenylenetriamine)
S stands for an N-structure element, which is the common component of groups P and F.

synthesis

4.0 g (13.9 mmol) of 2- (2,4-dinitrophenylamino) -2-hydroxymethylpropane-1,3-diol (hybrid dye 25) in a 1: 3 mixture of ethanol: water were added with the addition of 0.48 g Pd (5% on C) at room temp. hydrogenated. After about 1 h, 2030 ml of H _{2 had been} taken up, whereupon the reaction was stopped. 8 ml of cold dilute HCl were added, the solution was filtered under nitrogen and concentrated. The resulting residue was dried in vacuo at 50 ° C. Red crystals with melting point> 200 ° C (decomp.).
Yield: 12%. 5. Compounds based on polyhydroxycarboxylic acids 5.1. 2,3,4,5,6-pentahydroxyhexanoic acid (2- (2,4-dinitrophenylamino) ethyl) amide hybrid dye 16

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (2,4-dinitroaniline)
S stands for an ethylene group

synthesis

3.0 g (13.00 mmol) of N- (2-aminoethyl) -2,4-dinitroaniline and 2.4 g (13.00 mmol) of D (+) - gluconic acid δ-lactone were dissolved in 70 ml under nitrogen Ethanol taken up, heated to 60-64 ° C for 5 h and finally heated to boiling under reflux for 1 h. The reaction mixture was cooled and the suspension formed was suction filtered. The remaining residue was washed three times with EtOH, slurried, suctioned off and finally freeze-dried. Ocher powder with a melting point of 200 - 210 ° C.
Yield: 60% 5.2. 2,3,4,5,6-pentahydroxyhexanoic acid (2- (4-acetylamino-2-nitrophenylamino) ethyl) amide hybrid dye 17

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (4-acetylamino-2-nitroaniline)
S stands for an ethylene group

synthesis

1.5 g (6.00 mmol) of N- (4 - ((2-aminoethyl) amino) -3-nitrophenyl) acetamide and 1.1 g (6.00 mmol) of D (+) - gluconic acid δ-lactone were taken up in nitrogen in 40 ml of ethanol and heated at 60-65 ° C for 5 h. The reaction mixture was cooled and the suspension formed was suction filtered. The remaining residue was slurried four times with EtOH at 50 ° C., suction filtered and finally freeze-dried. Red powder with mp. 147-150 ° C (dec.).
Yield: 45% 5.3. 2,3,4,5,6-pentahydroxyhexanoic acid (2- (5-nitropyridin-2-ylamino) ethyl) amide hybrid dye 18

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (2-amino-5-nitropyridine)
S stands for an ethylene group

synthesis

10 g (55.0 mmol) of 2- (2-aminoethyl) amino-5-nitropyridine and 9.78 g (55.0 mmol) of D (+) - gluconic acid δ-lactone were taken up in 180 ml of ethanol under nitrogen and Heated to 60-65 ° C for 3.5 h. The reaction mixture was cooled and the suspension formed was suction filtered. The remaining residue was slurried three times with warm EtOH, suction filtered and finally freeze-dried.
Sand-colored powder with mp. 190-194 ° C (dec.).
Yield: 90% 5.4. 2,3,4,5,6-pentahydroxyhexanoic acid (2- (4-amino-2-nitrophenylamino) ethyl) amide hybrid dye 19

P derived from pentahydroxyhexanoic acid amide
F derived from a direct puller (2-nitro-p-phenylenediamine)
S stands for an ethylene group

synthesis

3.0 g (15.00 mmol) of N- (2-aminoethyl) - (4-amino-2-nitrophenyl) amine and 2.7 g (15.00 mmol) of D (+) - gluconic acid δ-lactone were added taken up in nitrogen in 70 ml of ethanol and heated to 60 ° C. for 4 h. The reaction mixture was cooled and the suspension formed was suction filtered. The remaining residue was washed with EtOH, then boiled with a little ethanol, filtered and finally freeze-dried. Violet powder with mp 175-177 ° C.
Yield: 64%

II. Colorings 1. Direct hybrid dyes

First, a cream base of the following composition was produced [unless otherwise stated, all information is in g]:
Hydrenol®D ¹ 17.00 Lorol®techn. ² 4.00 Eumulgin® B2 ³ 1.50 Texapon NSO ⁴ 30.00 Dehyton®K ⁵ 25,00 distilled water 22,50 ¹ C _16-18 fatty alcohol (INCI name: Cetearyl Alcohol) (COGNIS) ² C _12-18 fatty alcohol (INCI name: Coconut Alcohol) (COGNIS) ³ cetylstearyl alcohol + approx. 20 E0 (uNCI name: Ceteareth-20) (COGNIS) ⁴ Lauryl ether sulfate sodium salt (27.5% active substance; INCI name: Sodium Laureth Sulfate) (COGNIS) ⁵ N, N'-dimethyl-N (C ₈ -C ₁₈ cocosamidopropyl) ammonium acetobetaine (30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

Hydrenol®D, Lorol®techn., Eumulgin®B2, Texapon®NSO and Dehyton®K were added Melted 50 ° C, mixed with 80 ° C hot water and with vigorous stirring emulsified. The emulsion was then cooled with gentle stirring.

100 g of the following hair dye cream emulsion were then produced on the basis of this cream:
cream base 50,00 hybrid dye 1.00 (NH ₄ ) ₂ SO ₄ 1.00 25% ammonia solution ad pH 9.50 water ad 100.00

The cream base was melted at 85 ° C and the in dist. Water, ethanol, DMF or triethanolamine dissolved hybrid dye and that in max. 5 ml dist. Water dissolved Ammonium sulfate added. This mixture was distilled. Water made up to 97 g and adjusted to pH 9.5 with ammonia. Then was up to 100 g with dist. water filled up and the mixture stirred at <30 ° C until a homogeneous cream.

A strand of hair (Alkinco 6620; 330 to 370 mg) was well placed on a watch glass Mix embedded.

After 30 minutes, the strand of hair was treated with Texapon®EVR (INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis) washed until the excess color was removed. The strands of hair were then air dried and their shade under the Daylight lamp determined.

The results of the colorations are summarized in the following table:
hybrid dye Nuance of the dyed hair 1 bamboo yellow 2 nougat brown 3 naples yellow 6 gray ruby 8th ruby red-violet 11 violet brown 13 gray ruby 2-deoxy-2- (2,4-dinitrophenylamino) -α, β-D-glucopyranose neon yellow (fluorescent) 2-deoxy-2- (2,4-dinitrophenylamino) -1-O-methyl-α, β-D-glucopyranose olive yellow 2-deoxy-2- (2,4-dinitrophenylamino) -1-O-ethyl-α, β-D-glucopyranose grey yellow

2. Hybrid dye precursors

First, a cream base of the following composition was produced [unless otherwise stated, all information is in [g]:
tallow 7.0 Lorol®techn. ¹ 4.0 Texapon®N 28 ² 30.0 Dehyton®K ³ 25.0 Eumulgin®B 2 ⁴ 1.5 distilled water 12.5 ¹ C _12-18 fatty alcohol (COGNIS) ² sodium lauryl ether sulfate (approx. 28% active substance; INCI name: Sodium Laureth Sulfate) (COGNIS) ³ fatty acid amide derivative with betaine structure of the formula R-CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO ^- (approx. 30% active substance; INCI name Cocoamidopropyl Betaine) (COGNIS) ⁴ cetylstearyl alcohol with approx. 20 mol EO (INCI name: Ceteareth-20) (COGNIS)

The following hair dye cream emulsion was then produced on the basis of this cream:
cream base 50.0 developer component 7.5 mmol Kupplerkomponente 7.5 mmol Na ₂ SO ₃ (reducing agent) 1.0 (NH4) 2SO ₄ 1.0 water ad 100 Ammonia solution (25%) ad pH 10

The ingredients were mixed together in order. After adding the Oxidation dye precursors and the reducing agent were initially with 25% Ammonia solution the pH of the emulsion was adjusted to 10, then was with water made up to 100 g.

The oxidative development of the color was 1% or 9% Hydrogen peroxide solution carried out as an oxidation solution. For this purpose, 50 g of the emulsion were added mixed with 50 g of hydrogen peroxide solution and mixed.

The coloring creams were each applied to approx. 5 cm long strands of standardized, 80% gray but not specially pretreated human hair (from Kerling) and left there at 32 ° C. for 30 minutes. After the dyeing process was complete, the hair was rinsed, washed with a conventional shampoo and then dried. The following compounds were used as further dyes / dye precursors:
K1: resorcinol
K2: 1-naphthol

The results of the colorations are summarized in the following table:
III. Analysis of the nourishing hybrid dyes and / or hybrid dye precursors contained in the colorants according to the invention with regard to interstructurally stabilizing effects, leveling properties and color intensity

The review of the caring hybrid dyes and Colorants containing the hybrid dye precursors or the caring hybrid dyes and Hybrid dye precursors showed that these compared to the individual components, ie care component P or dye component F not linked to one another, clearly positive effects with regard to their internal structural stabilizing properties on the hair as well as with regard to their leveling and color intensity.

1. Investigation of the inner structural stabilizing properties of the invention nourishing hybrid dyes and hybrid dye precursors on the hair 1.1 Analysis method used HP-DSC (High Pressure Differential Scanning Calorimetry)

Thermal analysis is particularly suitable for the characterization of Two-phase systems, to which the human hair as a fiber keratin with its crystalline α-helix portion and amorphous matrix portion also belong. On the one hand you can Glass transitions and aging behavior of the amorphous matrix are examined on the on the other hand, the melting behavior of the crystalline, helical phase provides important Findings. Thermal analysis was first described in 1899, the first Differential thermal analyzes (DTA) on protein fibers were carried out in the late 1950s (F. Schwenker, J.H. Dusenbury, Text. Res. J. 1963, 30, page 800ff; W.D. Felix, M.A. McDowall, H. Eyring, ibid. (1963), 33, page 465ff.). In the following years are different thermoanalytical measuring methods, such as DTA, HP-DTA (High Pressure, high pressure DTA) and DSC (Differential Scanning Calorimetry, Dynamic Differential calorimetry), applied to keratin fibers to e.g. B. the phenomenon of Super contraction, a-β phase transitions of the helices or denaturation processes investigate. Recently, especially at the German Wool Research Institute in Aachen (F.J. Wortmann, H. Deutz, J. Appl. Polym. Sci. 1993, 48, page 137ff.), The Method used by HP-DSC to study keratin fibers that have problems with pyrolytic effects as they occur in conventional DSC and problems with excludes data collection and interpretation as contained in the DTA. In doing so DSC measurements on keratins carried out with water in commercially available, pressure-resistant measuring capsules are included. Develops in the keratin-water system when heated above 100 ° C in the encapsulated steel crucibles High pressure of water vapor, from which the HP-DSC analysis is derived. The serious one Difference of the HP-DSC thermograms of human hair compared to normal DSC thermograms is that of the endothermic peaks that meet the transformation point and reflect the enthalpy of conversion, here by approx. 90 ° C to lower temperatures are moved. This is because the water diffuses into the hair fiber Weakening and cleavage of hydrogen bonds and salt bonds Protein stability is reduced, thus lowering the "gluing temperature" of the keratins. Are only hydrogen bonds and the super-contracting agent like water Dissolved salt bridges, the thermal effect is reversible (super contraction). The However, the process becomes irreversible as soon as covalent bonds, such as. B. Disulfide bridges to be cleaved. This happens when you put human hair fibers in flameproof capsules heated to over 150 ° C with water. The irreversible transformation, interpreted as the transition of the α-helical regions in the proteins into a disordered one State, resulting in endothermic peaks, the peak location being the conversion or also denaturation point and the peak area the conversion or denaturation Enthalpy.

Accordingly, using Dynamic Difference Calorimetry (DSC) structural and chemical states and changes in fiber keratins and especially in human hair. Under precisely defined Test conditions can be used in human hair to determine the calorimetric processes using thermograms and record them with regard to the peak positions and structures and areas as indicators for influencing order-disorder transitions by changing internal and / or external parameters, z. B. by cosmetic treatment of hair, use. I.e. from the in the thermogram of Human hair recorded endothermic peaks can be due to peaking (Transformation point) and peak area (transformation enthalpy) statements about strength or damage the human hair fiber.

Detailed investigations regarding the influence of the cystine content on the Denaturation of the α-helices in keratins have e.g. B. shown that the denaturing Temperature (transition temperature) of keratin increases linearly with the cystine content. The increased stability of the matrix area due to the higher degree of crosslinking of the increased proportion of disulfide bridges in the matrix leads to the conversion of the into this matrix of embedded helices is made more difficult and thus results in an increase the denaturation temperature. Conversely, a denaturing Temperature and denaturation enthalpy reduction by perm or Bleaching or coloring of treated human hair can be observed (H. Deutz, Doctoral thesis, RWTH Aachen 1993).

1.2 Implementation using the example of the hybrid dye 6

• - 40 Min. Poly-Lock I - Dauerwelle (Schwarzkopf-Henkel)
• - 10 Min. Poly-Lock II Fixierung (Schwarzkopf-Henkel).

Standard Alkinco 6634 locks of hair (available from Alkinco Hair Company, New York, USA) were used. The previous damage was caused by the following treatment of the strand of hair:

• - 40 min. Poly-Lock I - perm (Schwarzkopf handle)
• - 10 min. Poly-Lock II fixation (Schwarzkopf handle).

The strands of hair pretreated in this way were then treated with aqueous solutions of the following composition according to Table 1:
Equimolar solutions (c = 2.8 mmol / 10 ml, corresponding to almost 1 g / 100 ml with respect to the hybrid dyes) were used in each case.

The pH of the solutions was basically determined using 0.1 molar NaOH or 0.1 molar HCl to 7.2.

The standard pre-damaged strands were immersed in 100 ml of solution. The exposure time was 30 minutes at 35 ° C. The strands were then 1.5 Rinsed under cold tap water for minutes and air dried at RT.

This was followed by the DSC measurements, which are shown in Table 1, and the evaluation using the parameter denaturation temperature of the keratin (peak maximum). Table 1 Inner structural stabilizing effects of the hybrid dye 6 at pH 7.2

Regarding the DSC thermolysis it should be noted that regarding the parameter Denaturation temperature hybrid dye 6 (strand 1) compared to the pure Reference (strand 4) induced an internal structural stabilizing effect (P> 98%). Furthermore, hybrid dye 6 induces only that in comparison to that Dye component F containing reference (strand 3) a significant structuring effect (P> 99%), as well as compared to that of a mixture of unlinked dye and care components F and P containing reference (Streak 2) (P> 99%).

This is a clear nourishing, structurally stabilizing effect of the Determine hybrid dye 6 containing colorant.

2. Examination of the color intensity and the leveling ability of the invention nourishing hybrid dyes and hybrid dye precursors on the hair using the example of Hybrid dyes 11 and 13

Standard Alkinco 6634 locks of hair (available from Alkinco Hair Company, New York, USA) were used. The previous damage was caused by the following treatment of the 15 cm long strand of hair:
upper part of the streak:
1 time:
Bleaching; Poly Blond Ultra (Schwarzkopf handle)
lower part of the streak:
2 times:
40 min. Poly-Lock I - perm (Schwarzkopf handle)
10 min. Poly-Lock II fixation (Schwarzkopf handle)
2 times: bleaching Poly Blond Ultra (Schwarzkopf-Henkel)

The standard leveling strands thus pretreated were then washed with aqueous Solutions of the following composition treated according to Table 2:

Equimolar solutions (c = 2.8 mmol / 100 ml, correspondingly almost 1 g / 100 ml with respect to the hybrid dyes) used, for better solubility each of the components 2% Eumulgin® B2 was added.

The pH of the solutions was adjusted to 6.9 using NaOH or HCl.

The standard pre-damaged leveling strands were in 10 ml solution immersed. The exposure time was 30 minutes at 35 ° C. Then the Strands rinsed under cold tap water for 1.5 minutes and at Air-dried at room temperature.

The colorimetric measurements of the color absorption or the color intensity for followed the upper and lower streak parts, respectively, which are shown in Tables 2 and 3 are.

The colorimetric measurement was carried out using a Texflash DC 3881 from Datacolor. The so-called CIE-Lab values were determined, from which the color differences result according to a color difference formula:

ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2

(see also DiN 6174, German standards, Benth Verlag GmbH, Berlin, 1975). The color intensities are calculated based on the following formula:

(K / S _sample ) / (K / S _reference ) × 100 = sample color strength [%]

with K = absorption coefficient, S = scattering coefficient, K / S = reflection coefficient Table 2 Color intensity of hybrid dyes 11 and 13 compared to corresponding references (upper part of the streak, normal weathered hair)

Table 3 Color intensity of hybrid dyes 11 and 13 compared to corresponding references (lower part of the streak, badly damaged hair)

In terms of color intensity, the streak with the highest color intensity was the same Set 100% and measure the corresponding comparison strands.

It should be noted that the hybrid dye 11 (galactose derivative) in comparison to the reference containing only the dye component F and to the one Mixture of unlinked dye and care components F and P containing Reference has a much more pronounced color intensity. This applies to both upper, as well as for the lower streak part.

The color intensity of hybrid dye 13 (lactose derivative) is also compared to the reference containing only the dye component F and also a mixture from unlinked dye and care components F and P containing Reference much more intense.

Furthermore, the leveling ability, i. H. the color deviations from the top to the lower part of the streak for hybrid dye 11 with regard to the parameters color depth, Red / green portion and yellow-blue portion determined.

The strands of hair and references described above were used here. The corresponding results are shown in Table 4. Table 4 Equalization of the hybrid dye 11 Comparison of upper and lower part of the highlights

If you compare the upper with the lower part of the hair strands with regard to the above parameters as an indicator of the equalization potential with each other, it can be seen that the hybrid dye hardly deviates between the upper and lower streak part and thus an excellent Equalization ability shows.

The leveling ability of the colorant containing the hybrid dye 11 is much better than that of a mixture of unlinked dye and Care components F and P containing reference and much better than that of only reference containing dye F.

Based on the results of the investigations regarding the color intensity and the Equalization ability of the hybrid dyes and / or Colorants containing hybrid dye precursors cannot therefore be only one clear nourishing effect, but also greatly improved coloring properties in the Comparison to the individual components can be determined.

Claims (11)

1. Agent for dyeing keratin fibers, characterized in that it contains, in addition to the constituents customary for such agents, at least one nourishing hybrid dye and / or at least one nourishing hybrid dye precursor of structure (I),

P - (S - F) _x (I)

in which x is an integer from 1 to 3; and
P stands for a care component,
F stands for a dye component; and
S stands for a structural element that is a common component of the groups P
and F is a direct bond or at least one spacer group. 2. Composition according to claim 1, characterized in that the care component P is derived from a compound selected from the group consisting of sugar, in particular glucose, mannose, galactose and / or allose, polyols, vitamins, in particular panthenol and derivatives thereof, amino acids, peptides, hydroxy acids and polyhydroxy acids and physiologically acceptable salts of the aforementioned Links. 3. Means according to claim 1 or 2, characterized in that the Dye component F is derived from a compound selected from the group comprising Coupling type oxidation dye precursors, oxidation dye precursors of the developer type, derivatives of indole or indoline as precursors of melanin, direct dyes, isatin and derivatives thereof and dyes that differ from as Derive dye and / or dye precursor suitable carbonyl compounds as well as physiologically acceptable salts of the aforementioned compounds. 4. Agent according to one of claims 1 to 3, characterized in that it continues one or more coupler or developer type oxidation dye precursors, one or more substantive dyes, one or more derivatives of indole or Indoline as a precursor of melanin, isatin and / or one or more derivatives of Isatin and physiologically acceptable salts of the aforementioned compounds contains. 5. Agent according to one of claims 1 to 4, characterized in that it is one or contains several surfactants selected from the group comprising anionic, zwitterionic, ampholytic, cationic and nonionic surfactants. 6. Agent according to one of claims 1 to 5, characterized in that it is one or contains several polymers selected from the group comprising cationic, anionic, nonionic and amphopolymer. 7. Use of an agent according to one of claims 1 to 6, for dyeing keratin fibers, especially human hair. 8. Use of an agent according to any one of claims 1 to 6, for dyeing the human skin. 9. Nourishing hybrid dyes and / or nourishing hybrid dye precursors according to structure (I) according to claim 1 for dyeing keratin fibers, characterized in that the dye component F
is selected from derivatives of indole or indoline as a precursor of melanin, from isatin and derivatives thereof or
is derived from carbonyl compounds suitable as a dye and / or dye precursor. 10. Nourishing hybrid dyes and / or nourishing hybrid dye precursors according to Structure (I) for dyeing keratin fibers, characterized in that the Care component P is derived from a compound selected from the group comprising sugar, in particular glucose, mannose, galactose and / or allose, Polyols, vitamins, especially panthenol and derivatives thereof, peptides, Hydroxy acids and polyhydroxy acids as well as physiologically acceptable salts of aforementioned connections. 11. Nourishing hybrid dyes and / or nourishing hybrid dye precursors according to Structure (I) for dyeing keratin fibers according to claim 10, characterized characterized in that the hybrid dyes or hybrid dye precursors are selected from the group comprising 2- (2,4-dinitrophenylamino) -2- hydroxymethylpropane-1,3-diol, 2- (2,4-diaminophenylamino) -2- hydroxymethylpropane-1,3-diol hydrochloride, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (2,4-dinitrophenylamino) ethyl) amide, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (4- acetylamino-2-nitrophenylamino) ethyl) amide, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (5-nitropyridin-2-ylamino) ethyl) amide, 2,3,4,5,6-pentahydroxyhexanoic acid- (2- (4- amino-2-nitrophenylamino) ethyl) amide, N- (4-allylamino-3-nitrophenyl) -2,3,4,6-O- tetraacetyl-α, β-D-glucopyranosylamine, N- (3-nitro-4-pyrrolidin-1-yl-phenyl) - 2,3,4,6-O-tetraacetyl-α, β-D-glucopyranosylamine, N- (4-allylamino-3-nitrophenyl) - α, β-D-glucopyranosylamine, N- (4-allylamino-3-nitrophenyl) -α, β- (4-β-D- galactopyranosyl) -D-glucopyranosylamine, N- (4-allylamino-3-nitrophenyl) -α, β-D- galactopyranosylamine, 2- (6-amino-4-carboxy-2-nitrophenylamino) -2-deoxy-α, β- D-glucopyranose, 2- (4-cyano-2,6-dinitrophenylamino) -2-deoxy-α, β-D- glucopyranose, 2- (4-carboxy-2,6-dinitrophenylamino) -2-deoxy-α, β-D- glucopyranose, N- (4-allylamino-3-nitrophenyl) -2-acetamido-2-deoxy-α, β-D- glucopyranosylamine, 1-O- (4-methyl-2-nitrophenylaminoethyl) -α, β-D- glucopyranose and N- (5-aminopyrid-2-yl) -α, β-D-glucopyranosylamine- Hydrochloride.