EP0910332A2

EP0910332A2 - Dyes

Info

Publication number: EP0910332A2
Application number: EP97931747A
Authority: EP
Inventors: Andreas Joachim Bittner; Astrid Kleen
Original assignee: Hans Schwarzkopf and Henkel GmbH
Current assignee: Hans Schwarzkopf and Henkel GmbH
Priority date: 1996-07-03
Filing date: 1997-07-02
Publication date: 1999-04-28
Also published as: JP2001501915A; WO1998001105A2; DE19728143A1; US20010052156A1; WO1998001105A3

Abstract

Agents for dyeing keratinic fibres contain as direct-dyeing agent a 4-nitroaniline derivative of formula (I), or a physiologically tolerable salt thereof with an inorganic or organic acid. In formula (I), R1, R2, R3 and R4 represent independently of each other a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulphalkyl, piperidinoalkyl, morpholinoalkyl or phenyl radical, which may be para-substituted by an amino group, these alkyl or alkoxy groups having 1 to 4 carbon atoms, provided that not all four substituents R1, R2, R3 and R4 simultaneously represent hydrogen. The groups -NR1-R2 and/or -NR3R4 may also represent an aziridine, azetidine, pyrrolidine, piperidine, azepan, azocin, morpholine, thiomorpholine or piperazine ring which may also bear at the nitrogen atom another substituent R8. R8 stands for a hydrogen atom, a (C1-C4)-alkyl, a hydroxy(C2-C3)-alkyl, a (C1-C4)-alkoxy-(C2-C3)-alkyl, an amino-(C2-C3)-alkyl or a 2,3-dihydroxypropyl group, and R5, R6 and R7 represent independently of each other a hydrogen atom, a halogen atom, a (C1-C4)-alkyl, a (C1-C4)-alkoxy radical, a carboxyalkyl, sulphalkyl or (C2-C4)-hydroxyalkyl radical. These compounds generate brilliant colours with high fastness. The number of tones may be further increased by adding other direct-dyeing agents or oxidation dye precursors.

Description

"Colorant"

The invention relates to agents for dyeing keratin fibers with special 4-nitroaniline derivatives as direct dyes.

In addition to so-called oxidation dyes, direct dyes are also used to dye keratin fibers. In contrast to the oxidation dyes, in which the dye precursors penetrate the hair and only form the actual dyes there under the influence of oxidizing agents, these dyes are able to dye the hair directly. Under the application-related boundary conditions (low dyeing temperature and short dyeing time) they result in intense colors with good fastness properties. The dyes diffuse into the fiber during the dyeing process. Nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols are usually used as direct dyes for dyeing keratin fibers. Such direct dyes for achieving a wide variety of shades, hereinafter referred to as direct pullers, play an important role in hair coloring. These dyes must give the desired color with sufficient intensity during the coloring, the colors obtained must have good light and acid fastness, and they must not tend to color shifts of the original shade under the wearing conditions. Furthermore, they should be dermatologically and toxicologically safe.

A large number of direct pullers for dyeing keratin fibers are already known. Red and yellow substantive dyes are disclosed, for example, in DE-AS 21 57 844 and DE-OS 33 23 207. However, these have some disadvantages. The solubility of these compounds, which plays an important role in perfect coloring, is very low. The luminosity and the color intensity of the colors obtained are also not sufficient.

There is therefore a constant need for new direct hair dyes, which are more and more demanding with regard to their light fastness, wash fastness and color depth, but also with regard to their toxicological and dermatological properties have to suffice. New direct pullers in the yellow and red areas of the color spectrum are particularly required for special yellow or bordeaux tones.

It was therefore the object of the present invention to provide new compounds which meet the requirements to be met by direct dyes to a particular degree.

Surprisingly, it has now been found that the compounds of the general formula (I) meet these requirements particularly well.

The present invention therefore relates to agents for dyeing keratin fibers which, as a direct dye, are a 4-nitroaniline derivative of the formula (I)

in which R ,, R ₂ , R ₃ and R ₄ independently of one another represent a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfalkyl, Piperidinoalkyl, morpholinoalkyl or a phenyl radical which is optionally substituted in para position with an amino group, these alkyl or alkoxy groups having one to four carbon atoms, with the proviso that not all four substituents R ₁ , R ₂ , R ₃ and R ₄ simultaneously represent hydrogen, and the groups -NR, R ₂ and / or -NR ₃ R _{4 can} also represent an aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, morpholine, thiomorpholine or a piperazine ring which can also carry a further substituent R ₈ on the nitrogen atom, where R _{g is} a hydrogen atom, a (C, -C ₄ ) alkyl, a hydroxy (C ₂ -C ₃ ) alkyl, a ( CC ₄ ) alkoxy- (C ₂ -C ₃ ) alkyl-, an amino- (C ₂ -C ₃ ) alkyl- or a 2,3-dihy is hydroxypropyl group, and R ₅ , R ^ and R ₇ independently of one another for a hydrogen atom, a halogen atom, a (C, -C ₄ ) alkyl, a (C, -C ₄ ) alkoxy radical, a carboxy, Are sulfo or a (C ₂ -C ₄ ) hydroxyalkyl radical, or contain a physiologically compatible salt of these compounds with an inorganic or organic acid. Keratin fibers are to be understood here as furs, wool, feathers and in particular human hair. Although the colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent their use in other areas.

The compounds of the formula (I) can be prepared by known processes. For this purpose, reference is expressly made to the explanations in the example section.

Particularly excellent dyeing properties are shown by compounds of the formula (I) in which the group -NR, R ₂ or -NR ₃ R _{4 is} aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, morpholine, Thiomorpholine or a piperazine ring, which can also carry a further substituent R ₈ on the nitrogen atom, where R _{8 is} a hydrogen atom, a (C, -C ₄ ) alkyl, a hydroxy (C ₂ -C ₃ ) alkyl -, is a (C, - C ₄ ) alkoxy- (C ₂ -C ₃ ) alkyl, an amino (C ₂ -C ₃ ) alkyl or a 2,3-dihydroxypropyl group.

Preferred substituents R 1 to R ₇ are, to the extent permitted by the general formula (I), hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-aminoethyl and 2,3-dihydroxypropyl groups, and for R ₅ to R ₇ halogen atoms.

Furthermore, those compounds of the formula (I) in which R and R _{2 are} not hydrogen are preferred, in which either R ₅ or R _{7 is} hydrogen. Also preferred are compounds of formula (I) in which R ₃ and R _{4 are} not hydrogen, in which R _{7 is} hydrogen.

The compounds of formula (I) can be used both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, e.g. the hydrochloride, the sulfate and hydrobromide. Other acids suitable for salt formation are phosphoric acid and acetic acid, propionic acid, lactic acid and citric acid. The statements made below on the compounds of the formula (I) therefore always include these salts.

The hair colorants according to the invention preferably contain the compounds of the formula (I) in an amount of 0.001 to 10% by weight, preferably 0.1 to 5% by weight, based in each case on the total colorant. Here and below, the "total colorant" is understood to mean the agent that is made available to the user. Depending on the form of formulation, this agent can either directly or, if the agent additionally contains oxidation dye precursors, after mixing with water or, for example, one aqueous solution of an oxidizing agent can be applied to the hair. +

According to a preferred embodiment, the agents according to the invention contain only the compounds of formula (I) as a dye component.

However, the number of available color shades is significantly increased if the agent contains, in addition to the compounds of the formula (I), a further direct dye or an oxidation dye precursor.

According to a second, likewise preferred embodiment, the colorants according to the invention contain, in addition to the compounds of the formula (I) according to Claim 1, optionally in addition to oxidation dye precursors, in addition to modifying the color shades, at least one further direct dye, e.g. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, Picramic Acid and Rodol 9 R known compounds and 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro - 1, 2,3,4-tetrahydroquinoxaline, (N-2,3-

Dihydroxypropyl-2-nitro-4-trifluoιτnethyl) amino-benzene and 4-N-ethyl-1, 4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride. The agents according to the invention in accordance with this embodiment preferably contain the further substantive dye in an amount of 0.01 to 20% by weight, based on the total colorant.

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

According to a third, likewise preferred embodiment, the agents according to the invention contain, in addition to the compounds corresponding to formula (I) according to Claim 1 and, if desired, substantive dyes and an oxidation dye precursor of the coupler type, at least one oxidation dye precursor of the developer type.

Preferred developer components according to the invention are p-phenylenediamine, p-toluylenediamine, p-aminophenol, 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis - (2-hydroxy-ethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, l-phenyl-3-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2 - Methylamino-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6, -triaminopyrimidine, 2,4-dihydroxy-5 , 6-diaminopyrimidine, 2-dimethyl__mino-4,5,6-triaminopyrimidine and 2-hydroxyethylaminomethyl-4-amino-phenol.

According to the invention, p-toluenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2-methylamino-4-aminophenol and 2,4,5 are very particularly preferred , 6-tetraaminopyrimidine.

Of course, this embodiment also includes the use of multiple developer components. Coupler combinations preferred according to the invention are

P-toluenediamine, p-phenylenediamine

• 3-methyl-4-aminoaniline, p-toluenediamine

P-toluenediamine, 4-amino-3-methylphenol

P-toluenediamine, 2-methylamino-4-aminophenol

• 2,4,5,6-tetraaminopyrimidine, 1- (2'-hydroxyethyl) -2,5-diaminobenzene

• 2,4,5,6-tetraaminopyrimidine, p-toluenediamine

According to a fourth, likewise preferred embodiment, the agents according to the invention contain, in addition to the compounds corresponding to formula (I) according to claim 1 and, if desired, further direct dyes and oxidation dye precursors of the developer type, at least one oxidation dye precursor of the coupler type.

Coupler components preferred according to the invention are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m- Phenylenediamine, l-phenyl-3-methyl-pyrazo-lon-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 4-chlororesorcinol, 2-chloro 6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihy- hydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diaminophenoxyethanol, 2-amino-4-hydroxyethylamino anisole.

According to the invention, 1,7-dihydroxynaphthalene, m-aminophenol, 2-methylresorcinol, 4-amino-2-hydroxytoluene, 2-amino-4-hydroxyethylamino-anisole and 2,4-diaminophenoxyethanol are particularly preferred. Of course, this embodiment also includes the use of multiple coupler components. Coupler combinations preferred according to the invention are

• resorcinol, m-phenylenediamine, 4-chlororesorcinol, 2-amino-4-hydroxyethylaminoanisole

• 2-methylresorcinol, 4-chlororesorcinol, 2-amino-3-hydroxypyridine

• resorcinol, m-aminoaniline, 2-hydroxy-4-aminotoluene

• 3-methyl-4-aminoaniline, m-aminoaniline, 2-hydroxy-4-aminotoluene, 2-amino-3-hydroxypyridine

• 2-methylresorcinol, m-aminoaniline, 2-hydroxy-4-aminotoluene, 2-amino-3-hydroxypyridine

Developer components and coupler components are usually used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can preferably be present in the colorant in a molar ratio of 1: 0.5 to 1: 2. The total amount of oxidation dye precursors is usually at most 20 wt .-%, based on the total agent.

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

Usual formulations for the oxidation coloring agents according to the invention are agents based on water or non-aqueous solvents as well as powders.

According to a preferred embodiment for producing the colorants according to the invention, the substantive dyes of the formula (I) and, if appropriate, further dyes and dye precursors are incorporated into a suitable water-containing carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, for example shampoos, aerosols or other preparations which are suitable for use on the hair. The colorants according to the invention are preferably adjusted to a pH of 6.5 to 11.5, in particular 9 to 10. Furthermore, the colorants according to the invention can contain all active substances, additives and auxiliaries known in such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants can be very particularly preferred.

Suitable anionic surfactants in the preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ether, amide and hydroxyl groups and generally also ester groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

linear and branched fatty acids with 8 to 22 carbon atoms (soaps), ether carboxylic acids of the formula RO- (CH2-CH2θ) _χ -CH2-COOH, in which R is a linear alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulphosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula

RO (-CH2-CH2θ) _χ -Sθ3 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 ether according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6

Double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, the additive

Products of about 2-15 molecules of ethylene oxide and / or propylene oxide

Represent 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 C8-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO - or -SO3 ^ 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 acylaminopropyl 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-aminoethyl-hydroxyethylcarboxymethylglycinate. 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 C8-C18-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-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkylimino dipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-18 acylsarcosine. 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 moles of ethylene oxide and / or 0 to 5 moles

Propylene oxide on linear fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to

22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,

C12-C22 fatty acid monoesters and diesters of adducts from 1 to 30 mol

Ethylene oxide on glycerol,

C8-C22 alkyl mono- and oligoglycosides and their ethoxylated analogues,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

Adducts of ethylene oxide with sorbitan fatty acid esters,

Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

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

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid S 18, are particularly notable for their good biodegradability. / O Quaternary ester compounds, so-called "esterquats", such as the dialkylammonium methosulfates and methyl-hydroxyalkyl-dialkoyloxyalkyl-ammonium-ethosulfates sold under the trademark Stepantex, are also very readily biodegradable.

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 the CTFA nomenclature a "Lauryl Methyl

Gluceth-10 hydroxypropyl dimonium chloride ".

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

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example

non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride -dimethyloloyl-methylenedilyl-sulfonyl-acrylamide-polymers, acrylamide-sulfonyl-methylenedi- lolamide-copolymerized with acrylamide Dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, II zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate

Copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,

Vinyl acetate / crotonic acid copolymers, vinylpyrrolidone-vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobornyl acrylate copolymers,

Methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans,

Cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and

Carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as e.g.

Polyvinyl alcohol,

Structurants such as glucose, maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin,

Egg lecithin and cephaline, as well as silicone oils,

Protein hydrolyzates, especially elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolyzates, their condensation products with

Fatty acids and quaternized protein hydrolyzates,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

Anti-dandruff agents such as Piroctone Olamine and Zink Omadine,

Alkalizing agents such as ammonia, monoethanolamine, 2-amino-2-methylpropanol and 2-amino-2-methyl-propanediol-1,3. other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts 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 like latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and

Air,

Antioxidants.

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; e.g. emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

If the agents according to the invention contain oxidation dye precursors, the oxidative development of the coloring can in principle take place with atmospheric oxygen or an oxidizing agent contained in the agent or added to it immediately before use.

According to a first embodiment, a chemical oxidizing agent is used. This is particularly advantageous in cases where, in addition to the coloring, a lightening effect on human hair is desired. Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or alkali borate. According to a particularly preferred variant of this embodiment, the colorant according to the invention is mixed with the preparation of the oxidizing agent, in particular an aqueous H ₂ O ₂ solution, immediately before use. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, such as a coloring shampoo, has been used.

In the case of hair that is difficult to dye, the preparation with the oxidation dye precursors can be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the - if necessary after an intermediate rinse / 3 Oxidation component applied. After a further exposure time of 10 to 20 minutes, rinsing is then carried out and, if desired, re-shampooing.

According to a second embodiment, the coloring takes place with atmospheric oxygen. It is advantageous to add an oxidation catalyst to the colorant according to the invention. Suitable oxidation catalysts are metal salts or metal complexes, with transition metals being preferred. Copper, manganese, cobalt, selenium, molybdenum, bismuth and ruthenium compounds are preferred. Copper (II) chloride, sulfate and acetate can be preferred oxidation catalysts. The complexes with ammonia, ethylenediamine, phenanthroline, triphenylphosphine, 1, 2-diphenylphosphinoethane, 1,3-diphenylphosphinopropane or amino acids can be preferred as metal complexes. Of course, it is also possible to use several oxidation catalysts in one agent. With regard to the production of suitable catalysts, reference is expressly made to the corresponding disclosure in EP 0 709 365 AI (page 4, lines 19 to 42), to which reference is expressly made.

It is also possible to carry out the oxidation with the aid of enzymes. The enzymes can be used both to produce oxidizing per compounds and to enhance the effect of a small amount of oxidizing agents present. An example of an enzymatic process is the procedure to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

Another object of the invention is the use of 4-nitroanilines of the general formula (I) according to claim 1 for dyeing keratin fibers.

The compounds of the general formula (I) can be converted by reducing the 4-nitro group into compounds of the general formula (Ia) in which a 4-amino group is present instead of the 4-nitro group

(la) '4- and R until R _{7 have} the same meaning as in the general formula (I). In the

Compounds of the general formula (Ia) can be converted into a substituted 4-amino group by alkylation or oxalkylation,

(Ib)

whereby compounds of the general formula (Ib) are obtained in which R until R _{7 have} the meaning given for the general formula (I) and R "and R ¹² independently of one another are a hydrogen atom, a (C, -C ₄ ) -alkyl -, a hydroxy (C ₂ -C ₃ ) alkyl, an alkoxy (C ₂ -C ₃ ) alkyl, an amino (C ₂ -C ₃ ) alkyl or a 2,3-dihydroxypropyl group can represent.

These compounds are oxidation dye precursors with particularly excellent coloring properties, which also have coupler and developer properties.

/ 5

B e i s p i e l e

1. General manufacturing processes 1.1a. Manufacturing process based on 2-nitroanilines

Compounds of the general formula (I) according to the invention in which R ₅ , R ^ and R _{7 are} hydrogen atoms can be prepared by 2-nitro-5-haloacetanilides of the general formula (II), in which X = fluorine, chlorine, bromine or Is iodine, with amines of the general formula (III), in which R 1 and R _{2 have} the meaning given in Claim 1, in an alkaline reaction medium, optionally with the addition of phase transfer catalysts, to correspondingly substituted 2-nitro-5-amino-anilines of the general Formula (IV) are implemented. This reaction can optionally be carried out in an autoclave under pressure if the boiling point of the amine is lower than the reaction temperature or the conversion is not complete. The products of the formula (IV) are hydrolyzed and, if appropriate, converted to the compounds of the general formula (I) by alkylation or oxalkylation. The compounds of the general formula (III) are common chemical raw materials and can be purchased. Suitable phase transfer catalysts are, for example, methyl or benzyl tri (C ₆ -

C ₈ ) alkyl ammonium chloride.

(II) (III) (IV)

(I)

According to a second process, compounds of the general formula (I) can be obtained by 5-halo-2-nitranilines of the general formula (V), where R ₃ and R _{4 have} the meaning given above, with amines of the general formula (III ) <r if appropriate with the addition of phase transfer catalysts to compounds of the general formula (I). This reaction can also optionally be carried out in an autoclave under pressure if the boiling point of the amine is lower than the reaction temperature or the conversion is not complete.

(V) (III) (I)

1.1b. Manufacturing process based on 4-nitroanilines

Compounds of the general formula (I) according to the invention in which R ₅ , R ^ and R _{7 are} hydrogen atoms can also be prepared by 2-nitro-5-acetylaminohalogenbenzenes of the general formula (II) ', in which X = fluorine, Is chlorine, bromine or iodine, with amines of the general formula (III) ', in which R ₃ and R _{4 have} the meaning given above, in an alkaline reaction medium, optionally with the addition of phase transfer catalysts, to optionally substituted 2-nitro-5-acetylamino-aniline NEN of the general formula (IV) 'are implemented. This reaction can optionally be carried out in an autoclave under pressure if the boiling point of the amine is lower than the reaction temperature or the conversion is not complete.

(II) '(HI)' (IV) '

The compounds of the formula (IV) 'are hydrolyzed to the compounds of the general formula (V) and, if appropriate, converted to the compounds of the general formula (I) according to the invention by alkylation or oxalkylation. The compounds of the general formula (III) 'are customary chemical raw materials and can be bought '7 can be acquired. Suitable phase transfer catalysts are, for example, methyl or benzyl tri (C ₆ -C ₈ ) alkylammonium chloride.

(IV)

hydrolysis

(V) '(I) R ⁵ , R ⁶ and R ⁷ = H

According to a second process, compounds of the general formula (I) according to the invention are prepared by using substituted 2-nitro-4-aminohalobenzenes of the general formula (VI) ', in which X = fluorine, chlorine, bromine or iodine and R ₃ and R ₄ are have the meaning given above, with amines of the general formula (III) ', in which R ₁ and R _{2 have} the meaning given above, in an alkaline reaction medium, optionally with the addition of phase transfer catalysts, to substituted 2-nitro-4-aminoanilines of the general formula ( I) be implemented. This reaction can also optionally be carried out in an autoclave under pressure if the boiling point of the amine is lower than the reaction temperature or the conversion is not complete.

(VI) '(III)' (I) R \ R ⁶ and R ⁷ = H

For the oxyalkylation, the compounds of the general formula (V) 'for which R ₁ and R ₂ = hydrogen are in an inert solvent with 2-chloroethyl chloroformate (VII) (R, = CH ₂ CH ₂ C1) or chloroformic acid 3-chloropropyl ester (VII) (Re = CH ₂ CH ₂ CH ₂ C1) converted into compounds of the general formula (VIII) '. The intermediates of the general O 98/01105

/ g

(V) '(VII) (VIII)'

Formula (VIII) 'are then with strong bases, for. B. sodium or potassium hydroxide to compounds of the general formula (IX) 'in which R ₁₀ = CH ₂ CH ₂ OH or CH ₂ CH ₂ CH ₂ OH means that with known alkylating or oxyalkylating agents

(VIII) '(IX)'

React products of the general formula (I), in which R 1 to R _{4 have} the meaning already indicated, and if appropriate converts them with an inorganic or organic acid into their salt.

According to a third process, compounds of the general formula (I) according to the invention can be obtained by 3-halo-4-nitranilines of the general formula (VI) with amines of the general formula (purple), where R 1 to R _{4 have} the meaning given above have, optionally with the addition of phase transfer catalysts to compounds of the general formula (I).

After the function X has been replaced by NR, R ₂ or NR ₃ R ₄ and, if appropriate, further alkylation or oxalkylation, compounds of the general formula (I) according to the invention are then obtained and these are optionally converted into their salt with an inorganic or organic acid.

1.2. General comments on the manufacturing process

The first stage of the above-mentioned processes consists in principle of replacing a halogen substituent with an amine substituent on the phenyl ring. In the known processes, an amine excess of about 40-80% is usually used; the products are obtained in yields of approx. 90% and with a purity of 95-96%. Surprisingly, it has now been found that higher yields with the same or better purity and faster conversion can be achieved if the amine excess is 30% and less, in particular 5 to 10 mol%, based on the amounts of the compound of the formula (II) used, (V ), (VI), (II) 'or (VI)'. It is also preferred to carry out the reaction in an organic solvent. The reaction is preferably carried out under a pressure of from 1 to 15 bar, in particular from 1 to 8 bar and very particularly preferably from 1 to 2.5 bar.

For example, methyl or benzyl tri (C ₆ -C ₈ ) alkylammonium chlorides or tetraphenylphosphinium chloride can be used as phase transfer catalysts.

For salt formation, for example, hydrochloric acid, sulfuric acid or phosphoric acid are suitable as inorganic acids and acetic acid, propionic acid, lactic acid or citric acid as organic acids.

For the oxyalkylation, the compounds of the general formula (I) for which R ₃ and R ₄ = hydrogen are, according to known processes, in an inert solvent with 2-chloroethyl chloroformate (R <, = CH ₂ CH ₂ C1) or chloroformate. 3-chloropropyl ester (VII) (R_, = CH ₂ CH ₂ CH ₂ C1) in compounds of the formula (VIII)

(I) R ₃ and R ₄ = H (VII) (VIII) 2.0 convicted. The intermediates of formula (VIII) are then with strong bases, for. B. sodium or potassium hydroxide, to compounds of general formula (IX)

(VIII) (IX)

implemented, wherein R _I0 = CH ₂ CH ₂ OH or CH ₂ CH ₂ CH ₂ OH, which react with known alkylating or oxyalkylating agents to give products of the general formula (I), in which R to R _{4 are} the same as those already given Have meaning, and optionally converted into an inorganic or organic acid in the salt thereof.

1.3. Preparation of special compounds according to formula (I)

The compounds produced were characterized by IR or IR (KBr compact) and / or 'H NMR spectra (in D ₆ -DMSO). As far as the spectra are given here, only the very strong and strong bands are listed for the IR spectra. In the data on the 'H NMR spectra, s singlet, d doublet, dd doublet from the doublet, t triplet, q quartet, qi quintet, m multiplet, ³ J and ⁴ J mean the couplings via three and four bonds respectively H ² , H ³ , H \ H ⁵ and H ^{6 represent} the hydrogen atoms in positions 2, 3, 4, 5 and 6 of the benzene ring.

1.3.1. Preparation of N, N-dimethyl-3-amino-4-nitroaniline Step a) N, N-Dimethyl-4-nitro-3-acetaminoanüin

100 ml of 1,2-dimethoxyethane, 21.5 g (0.1 mol) of 5-chloro-2-nitroacetanilide, 20.7 g (0.15 mol) of potassium carbonate and 16.9 g (0.15 Mol) submitted 40% dimethylamine solution; this mixture was heated to 120 ° C. with stirring for eight hours, the inorganic salts were filtered hot and the solvent was removed in vacuo. The precipitated yellow powder was recrystallized from ethanol.

Yield: 21.3 g (95.4% of theory)

IR: 3313 cm ^'1 (v CH, 3313, 3143, 2927 cm ^"1 (v CH), 1702 cm ^{" 1} (v C = O), 1622 cm ^"1 (v C = C), 1575, 1548 cm ^{" 1} (v _M NO ₂ ), 1344, 1310 cm ^"1 (v _f NO ₂ ). 'H NMR: 10.59 ppm (1H, s, NHAc); 8.02 ppm (H \ d, ³ J _HH = 9.70 Hz); 7.63 ppm

(H ² , d, ⁴ J _HH = 2.71 Hz); 6.54 ppm (H ⁶ , dd, ³ J _HH = 9.57 Hz, ⁴ J _HH = 2.55 Hz);

3.07 ppm (6H, s, N (CH ₃₎ _2); 2.17 ppm (3H, s, C (= O) CH ₃ ). Step b) N, N-dimethyl-3-amino-4-nitroanüin

20.3 g (0.091 mol) of N, N-dimethyl-4-nitro-3-acetaminoaniline (from stage a) were placed in a mixture of 75 ml of water and 21 ml of methanol and the mixture was treated with 20.7 ml of concentrated hydrochloric acid for one hour Reflux heated. After conversion was complete, the pH of the mixture was adjusted to 7 with aqueous ammonia and the product was stirred, suction filtered and washed with water. Yield: 15.9 g (96.4% of theory)

IR: 3468, 3348 cm ^'1 (v CH, 2922 cm ^"1 (v CH), 1619 cm ¹ (v C = C), 1557 cm ^"

'(v _as NO ₂ ), 1312 cm ^" ' (v _s NO ₂ ). 'H-NMR: 7.82 ppm (H ⁵ , d, ³ J _HH = 9.75 Hz); 7.25 ppm (2H , s, NH ₂ ); 6.20 ppm (H ⁶ , dd, ³ J _HH = 9.81 Hz, ⁴ J _HH - 2.68 Hz); 5.96 ppm (H ² , d, J _HH = 2 , 67 Hz); 3.00 ppm (6H, s, N (CH ₃ ) ₂ ).

1.3.2. Preparation of N- (4-nitro-3-aminophenyl) morpholine stage a) N- (4-nitro-3-acetaminophenyl) morpholine

Stage a) was carried out analogously to Example 1.3.1. Step a) by reacting 5-chloro-2-nitroacetanilide with morpholine.

Yield: 24.1 g (90.8% of theory) of yellow crystals

IR: 3438 cm ^" '(v CH, 3312, 3140, 2973, 2855 cm ^" ' (v CH), 1698 cm ^" '(v

C = O), 1617 cm ^" '(v C = C), 1580 cm ^" ' (v ,, NO ₂ ), 1312 cm ^'1 (v _s NO ₂ ). 'H NMR: 10.43 ppm (1H, s, NHAc); 7.98 ppm (H ⁵ , d, ³ J _HH = 9.55 Hz); 7.70 ppm

(H ² , d, J _aH = 2.69 Hz); 6.78 ppm (H ⁶ , dd, ³ J _HH = 9.59 Hz, J _HH = 2.72 Hz);

3.73 ppm (4H, t, ³ J _RH = 4.85 Hz, N (CH ₂ CH ₂ ) ₂ O); 3.35 ppm (4H, t, ³ J _HH =

4.91 Hz, N (CH ₂ CH ₂ ) ₂ O); 2.15 ppm (3H, s, C (= O) CH ₃ ). Step b) N- (4-nitro-3-aminophenyl) morpholine

The preparation in stage b) was carried out analogously to Example 1.3.1. Step b) by reaction of N- (4-nitro-3-acetaminophenyl) morpholine with hydrochloric acid. Yield: 15.3 g (84.4% of theory)

1.3.3. Preparation of N-methyl-2-nitro-5-aminoaniline Step a) N-Methyl-2-nitro-5-acetaminoaniline

In an autoclave, 100 ml of 1,2-dimethoxyethane, 21.5 g (0.1 mol) of 3-chloro-4-nitroacetanilide, 15.1 g (0.1 1 mol) of potassium carbonate and 12.4 g (0.05 11 mol) 40% methylamine solution submitted; this mixture was heated with stirring for eight hours to 120 ° C, filtered hot from the inorganic salts and removed the solvent in

Vacuum. The precipitated yellow powder was recrystallized from ethanol.

Yield: 17 g (100% of theory)

IR: 3351 cm ^"1 (v CH, 3303, 3183, 2808 cm ^'1 (v CH), 1694 cm ^{" 1} (v C = O),

1639 cm- '(v C = C), 1582, 1562 cm ^"1 (v _as NO ₂ ), 1366, 1325 cm ^{" 1} (v _s NO ₂ ). 'H NMR: 10.2 ppm (1H, s, NHAc); 8.43 ppm (1H, m, NHCH ₃ ); 8.19 ppm (H \ d,

³ J _{H> H} = 9.34 Hz); 7.56 ppm (H ⁶ , d, J _HH = 2.95 Hz); 6.97 ppm (H ⁴ , dd, ³ J _HH

= 9.42 Hz, ⁴ J _H. _H = 2.14 Hz); 3.08 ppm (3H, t, ³ J _HH = 4.93 Hz, NCH ₃ ); 2.27 ppm (3H, s, C (= O) CH ₃ ). Step b) \ -J-methyl-2-nitro-5-aminoaniline

15.9 g (0.095 mol) of 3-methylamino-4-nitroacetanilide (from stage a) were placed in a mixture of 78 ml of water and 26 ml of methanol and refluxed for one hour with 25.8 ml of concentrated hydrochloric acid. After conversion was complete, the pH of the mixture was adjusted to 7 with aqueous ammonia, the product was stirred, suction filtered and washed with water. Yield: 12.4 g (78.1% of theory)

IR: 3425 cm ^"1 (v CHJ, 3336, 3227, 2926 cm ^{" 1} (v CH), 1636 cm ^"1 (v C = C),

1577 cm ^" '(v _M NO ₂ ), 1331 cm ^" ' (v, NO ₂ ). 'H NMR: 8.33 ppm (1H, m, NHCH ₃ ); 7.82 ppm (H ³ , d, ³ J _HH = 9.37 Hz); 6.59 ppm

(2H, s, NH ₂ ); 6.0 ppm (H \ dd, ³ J _HH = 9.36 Hz, ⁴ J _HH = 2.12 Hz); 5.8 ppm

(H ⁶ , d, ⁴ J _{H, H} = 2.11 Hz); 2.86 ppm (3H, t, _JH . _H = 4.96 Hz, NCH ₃ ).

1.3.4. Preparation of N-ethyl-2-nitro-5-aminoaniline

Step a) N-ethyl-2-nitro-5-acetaminoaniline

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with ethylamine.

Yield: 19.7 g (88.2% of theory) of yellow crystals

IR: 3343 cm ¹ (v CHJ, 3225, 2971, 2873 cm ^'1 (v CH), 1702 cm ^" ' (v C = O),

1621 cm ^'1 (v C = C), 1582 cm ^{' 1} (v. NO ₂ ), 1367 cm ^'1 (v _s NO ₂ ).

'H NMR: 10.31 ppm (1H, s, NHAc); 8.19 ppm (1H, t, NHEt, ³ J _HH = 5.22 Hz); 8.02 ppm (H \ d, ³ J _H, "= 9.42 Hz); 7.46 ppm (H ⁶ , d, ⁴ J _{H, H} = 1.97 Hz); 6.79 ppm (H ⁴ , dd, ³ J _{H, H} = 9.39 Hz, ⁴ J _H. _H = 2.01 Hz); 3.08 ppm (2H, m, ³ J _{H CH3} = 5.71 Hz, ³ J _CH2 . _CH3 = 6.99 Hz, NCH ₂ ); 1.25 ppm (3H, t, ³ J _HH = 7.11 Hz, NCH ₂ CH ₃ ).

Step b) N-ethyl-2-nitro-5-aminoaniline

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N-ethyl-2-nitro-5-acetaminoaniline with hydrochloric acid.

Yield: 15.3 g (84.4% of theory) 2.3

IR: 3438 cm ^'1 (v CH, 3339, 3232, 2979 a ¹ (v CH), 1619 cm ^" ' (v C = C). 1564 cm ^" '(v _as NO ₂ ), 1354 cm ^" ' (v _s NO ₂ ).

'H NMR: 8.29 ppm (1H, s, NH); 7.82 ppm (H ³ , d, ³ J _HH = 9.22 Hz); 6.59 ppm (2H, s, NH ₂ ); 6.0 ppm (H \ dd, ³ J _{H, H} = 9.48 Hz, ⁴ J _HH = 2.0 Hz); 5.84 ppm (H ⁶ , d, ⁴ J _H. _H = 2.03 Hz); 3.2 ppm (2H, m, ³ J _{H CH3} = 5.45 Hz, ³ J _CH2, c _H3 = 7.08 Hz, NCH ₂ ); 1.24 ppm (3H, t, ³ J _{CH2, CH3} = 7.12 Hz, NCH ₂ CH ₃ ).

1.3.5. Preparation of N-n-propyl-2-nitro-5-aminoaniline

Step a) N-n-propyl-2-nitro-5-acetylaminoaniline

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with «-propylamine.

Yield: 15.5 g (65.3% of theory) of yellow crystals IR: 3349 cm ^" '(v CH, 3235, 2964, 2934 cm ^{" 1} (v CH), 1694 cm ^" ' (v C = O ),

1623 cm ^" '(v C = C), 1582 cm ^{' 1} (v _ω NO ₂ ), 1326 cm ^" '(v _s NO ₂ ).

'H NMR: 10.30 ppm (1H, s, NHAc); 8.25 ppm (1H, t, NHPr, ³ J _HH = 5.40 Hz); 8.02 ppm (H \ d, ³ J _HH = 9.35 Hz); 7.46 ppm (H ⁶ , d, J _HH = 2.08 Hz); 6.78 ppm (H \ dd, ³ J _HH = 9.39 Hz, J _{H> H} = 2.14 Hz); 3.22 ppm (2H, m, NCH ₂ ); 2.09 ppm (3H, s, C (= O) CH _3); 1.65 ppm (2H, m, NCH ₂ CH ₂ CH ₃ ); 0.96 ppm (3H, t, ³ J _{H, H} = 7.40 Hz, NCH ₂ CH ₂ CH ₃ ).

Step b) N-n-propyl-2-nitro-5-aminoaniline

The preparation in stage b) is carried out analogously to example 1.3.3. Step b) by reaction of N-_7-propyl-2-nitro-5-acetaminoaniline with hydrochloric acid.

Yield: 1 1.7 g (98.3% of theory) IR: 3444 cm ^" '(v CH, 3343, 3232, 2964 cm ^{" 1} (v CH), 1631 cm ^"1 (v C = C) ,

1570 cm ^" (v _β NO ₂ ), 1364 cm ^" '(v, NO ₂ ).

'H NMR: 8.38 ppm (1H, t, ³ J _HH = 4.67 Hz, NH); 7.84 ppm (H ³ , d, ³ J _HH = 9.36 Hz);

6.59 ppm (2H, s, NH ₂ ); 6.02 ppm (H ⁴ , dd, ³ J _HH = 9.38 Hz, ⁴ J _{H, H} = 1.81 Hz);

5.86 ppm (H ⁶ , s); 3.16 ppm (2H, m, ³ J _HH = 7.21 Hz, NCH ₂ ); 1.64 ppm (2H, t, ³ J _HH = 7.37 Hz, NCH ₂ CH ₂ CH ₃ ); 0.97 ppm (3H, t, ³ J _HH = 7.37 Hz,

NCH ₂ CH ₂ CH ₃ ).

1.3.6. Preparation of N- \ so-butyl-2-nitro-5-aminoaniline stage a) N-iso-butyl-2-nitro-5-acetylaminoaniline

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with wo-butylamine. Yield: 14.5 g (57.7% of theory) of yellow crystals

IR: 3347 cm ^" '(v CH, 3083, 2969, 2936 cm ^{' 1} (v CH), 1704, 1680 cm ^{" 1} (v

C = O), 1621 cm ¹ (v C = C), 1581 cm ^"1 (v _u NO ₂ ), 1325 cm ^{" 1} (v _s NO ₂ ). 'H NMR: 10.31 ppm (1H, s, NHAc); 8.09 ppm (1H, t, NHBu, ³ J _H = 7.51 Hz); 8.08 ppm (H ³ , d, ³ J _a "= 9.38 Hz); 7.53 ppm (H ⁶ , d, ⁴ J _HH = 2.01 Hz); 6.78 ppm (H ⁴ , dd, ³ J _aH = 9.38 Hz, J _aH = 2.09 Hz); 3.53 ppm (1H, q, CH (CH ₃₎ _2); 2.1 ppm (3H, s, C (= O) CH _3); 1.61 ppm (2H, m, ³ J _aH = 7.09 Hz, NCH ₂ (CH ₃ ) ₂ ); 1.24 ppm (3H, d, ³ J _aH = 6.34 Hz, syn-CH (CH ₃ ) ₂ ); 0.94 ppm (3H, t, ³ J _aH = 7.42 Hz, anti-CH (CH ₃ ) ₂ ).

Step b) N-iso-butyl-2-nitro-5-aminoaniline

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N-wo-butyl-2-nitro-5-acetaminoaniline with hydrochloric acid.

Yield: 11.5 g (55.2% of theory)

Melting point: (red oil)

IR: 3467, 3350, 3234 cm ^" '(v CH, 2967, 2932, 2876 cm ^" ' (v CH), 1631 cm ^"1

(v C = C), 1568 cm ^'1 (v _as NO ₂ ), 1355 crn' (v _s NO ₂ ).

'H NMR: 8.33 ppm (1H, d, ³ J _HH = 7.56 Hz, NH); 7.82 ppm (H ³ d, ³ J _aH = 9.46 Hz); 6.00 ppm (H \ dd, ³ J _HH = 9.48 Hz, ⁴ J _aH = 2.18 Hz); 5.87 ppm (H ⁶ , d, ⁴ J _H = 2.11 Hz); 3.49 ppm (1H, m, ³ J _H = 6.56 Hz, NCH-CH); 1.59 ppm (2H, m, ³ J _H = 9.21 Hz, NCH ₂ CH (CH ₃ ) ₂ ); 1.21 ppm (3H, d, ³ J _HH = 6.33 Hz, anti-NCH ₂ CH (CH ₃ ) ₂ ); 0.93 ppm (3H, t, J _HH = 7.44 Hz, syn-NCH ₂ CH (CH ₃ ) ₂ ).

1.3.7. Preparation of N, N-dimethyl-2-nitro-5-aminoaniline

Step a) N, N-dimethyl-2-nitro-5-acetylaminoaniline

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with dimethylamine.

Yield: 16.8 g (75.5% of theory) of yellow crystals IR: 3552, 3363 cm ^'1 (v CH, 2928, 2801 cm ^"1 (v CH), 1678 cm ^" ' (v C = O ),

1613 cm ^'1 (v C = C), 1554 cm ^"1 (v .. NO ₂ ), 1337 cm ^{' 1} (v _s NO ₂ ).

'H NMR: 10.2 ppm (1H, s, NHAc); 7.8 ppm (H ³ , d, ³ J _H, "= 9.02 Hz); 7.48 ppm (H ⁶ , d, ⁴ J _H = 1.83 Hz); 7.05 ppm (H ⁴ , dd, ³ J _aH = 9.03 Hz, ⁴ J _HH = 1.98 Hz); 2.08 ppm (3H, s, C (= O) CH _3); 2.78 ppm (6H, s, N (CH ₃₎ _2). Step b) N, N-dimethyl-2-nitro-5-aminoaniline

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N, N-dimethyl-2-nitro-5-acetaminoaniline with hydrochloric acid. Yield: 18.9 g (100% of theory) of yellow crystals

IR: 3449, 3337 cm ^" '(v CH, 2971, 2872 cm ¹ (v CH), 1619 cm ^" ' (v C = C),

1562 cm ^"1 (v, NO ₂ ), 1320 cm ^'1 (v _s NO ₂ ).' H-NMR: 7.83 ppm (H \ d, ^ = 9.70 Hz); 7.29 ppm ( 2H, s, NH ₂ ); 6.38 ppm (H ⁴ , dd, ³ J _HH = 9.76 Hz, ⁴ J _Hii = 2.60 Hz); 6.23 ppm (H ⁶ , d, ⁴ J _H = 2.60 Hz); 3.71 -fc5 ppm (3H, t, ³ J _HH = 4.88 Hz, syn-NCH ₃ ); 3.27 ppm (3H, t. ³ J _HH = 4.90 Hz, anti-NCH ₃ ).

1.3.8. Preparation of N, N-diethyl-2-nitro-5-aminoaniline

Step a) N, N-diethyl-2-nitro-5-acetylaminoaniline

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with diethylamine.

Yield: 20.1 g (79.9% of theory) of yellow crystals

IR: 3437, 3294 cm ^" '(v CH, 2979, 2934 cm ^" ' (v CH), 1671 cm ^'1 (v C = O),

1613 cm ^" '(v C = C), 1558 cm ^" ' (v ^ NO ₂ ), 1347 cm '(v _s NO ₂ ).

'H NMR: 10.43 ppm (1H, s, NHAc); 7.92 ppm (H ³ , d, J _aH = 9.24 Hz); 7.75 ppm

(H ⁶ , d, J _aH = 2.06 Hz); 7.35 ppm (H \ dd, ³ J _HH = 8.97 Hz, ⁴ J _aH = 2.06 Hz);

3.26 ppm (4H, q, ³ J _aH = 7.04 Hz, N (CH ₂ CH ₃ ) ₂ ); 2.26 ppm (3H, s,

C (= O) CH ₃ ); 1.20 ppm (6H, t, ³ J _H = 7.04 Hz, N (CH ₂ CH ₃ ) ₂ ).

Step b) N, N-diethyl-2-nitro-5-aminoaniline

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N, N-DiethyI-2-nitro-5-acetaminoaniline with hydrochloric acid.

Yield: 12.6 g (60.2% of theory)

Melting point: (red oil)

IR: 3469, 3367, 3233 cm ^'1 (v CH, 2974, 2923, 2872 cm ^"1 (v CH), 1631 a ¹

(v C = C), 1567 cm ^"1 (v ,, NO ₂ ), 1344 cm ^" '(v _s NO ₂ ).

'H NMR: 7.91 ppm (H ³ , d,% _M = 8.99 Hz); 6.45 ppm (2H, s, NH ₂ ); 6.41 ppm (H ⁶ , d,

⁴ J _a "= 2.23 Hz); 6.32 ppm (H \ dd, ³ J _aH = 9.08 Hz, ⁴ J _aH = 2.23 Hz); 3.23 ppm (3H, t, ³ J " _{, H} = 7.04 Hz, N (CH, CH ₃ ) ₂ ); 1.21 ppm (3H, t, ³ J _H = 7.03 Hz, N (CH ₂ CH ₃ ) ₂ ).

1.3.9. Preparation of N- (5-amino-2-nitrophenyl) pyrrolidine

Step a) N- (5-acetylamino-2-nitrophenyl) pyrrolidine

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with pyrrolidine.

Yield: 24.3 g (97.5% of theory) of yellow crystals

IR: 3262 cm ^"1 (v CH, 2969, 2873 cm ^{" 1} (v CH), 1667 cm ^"1 (v C = O), 1614 cm ^" ¹ (v C = C), 1548 cm ^"1 (v ^ NO ^, 1358 cm ^'1 (v _s NO ₂ ).' H NMR: 10.38 ppm (1H, s, NHAc); 7.91 ppm (H \ d, ³ J _HH = 9.05 Hz); 7.61 ppm

(H ⁶ , d, ⁴ J _aH = 1.95 Hz); 7.11 ppm (H ⁴ , dd, ³ J _aH = 9.06 Hz, ⁴ J _H = 2.01 Hz);

3.27 ppm (4H, t, ³ J _H = 6.25 Hz, N (CH ₂ ) ₂ ); 2.25 ppm (3H, s, C (= O) CH ₃ );

2.09 ppm (4H, t, ³ J _aH = 6.25 Hz, Step b) N- (5-amino-2-nitrophenyl) pyrrolidine _. <f

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyl) pyrrolidine with hydrochloric acid.

Yield: 18.3 g (98.1% of theory)

Melting point: (red oil)

IR: 3468, 3366, 3231 a '(v CH, 2970, 2874 cm ^{' 1} (v CH), 1608 cm ^"1 (v

C = C), 1560 cm ^" '(v _κ NO ₂ ), 1360 cm ^{" 1} (v _s NO ₂ ). 'H NMR: 7.81 ppm (H \ d, ³ J _{H> H} = 9.35 Hz); 6.32 ppm (2H, s, NH ₂ ); 6.18 ppm (HH ⁶ , m); 3.25 ppm (4H, t, J _aH = 6.34 Hz, N (CH ₂ CH ₂ ) ₂ ); 2.05 ppm (4H, t, ³ J _HH =

6.35 Hz, N (CH ₂ CH ₂ ) ₂ ).

1.3.10. Preparation of N- (5-amino-2-nitrophenyl) piperidine Step a) N- (5-acetylamino-2-nitrophenyl) piperidine

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with piperidine.

Yield: 22.1 g (84.1% of theory) of yellow crystals

Step b) N- (5-amino-2-nitrophenyl) piperidine

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyI) piperidine with hydrochloric acid.

Yield: 17.8 g (81.5% of theory)

Melting point: (red oil)

IR: 3449, 3358, 3245 cm ^" '(v CH, 2990, 2938 cm ^{" 1} (v CH), 1604 cm ^{' 1} (v

C = C), 1563 cm ^"1 (v ^ NO _j ), 1341 cm ^'1 (v _s NO ₂ ).

'H NMR: 7.83 ppm (H ³ , d, ³ J _H = 8.91 Hz); 6.40 ppm (2H, s, NH ₂ ); 6.19 ppm (H ⁴ , dd, ³ J _aH = 4.36 Hz, J _H = 2.19 Hz); 6.15 ppm (H ⁶ , d, ⁴ J _HH = 2.29 Hz); 2.88 ppm (4H, t, ³ J _HH = 5.37 Hz, N (CH ₂ CH ₂ ) ₂ CH ₂ ); 1.63 ppm (4H, m, N (CH ₂ CH ₂₎ ₂ CH _2); 1.54 ppm (2H, m, N (CH ₂ CH ₂ ) ₂ CH ₂ ).

1.3.11. Preparation of N- (5-amino-2-nitrophenyl) azepane Step a) N- (5-Acetylamino-2-nitrophenyl) azepane

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with azepane.

Yield: 25.3 g (91.3% of theory) of yellow crystals

IR: 3331, 3285 cm ^'1 (v CH, 2934, 2856 cm ^"1 (v CH), 1700, 1681 cm ^" ' (v

C = O), 1613 cm ^"1 (v C = C), 1549 cm ^{" 1} (v _M NO ₂ ), 1338 cm ^"1 (v _s NO ₂ ).

'H NMR: 10.2 ppm (1 H, s, NHAc); 7.70 ppm (H ³ , d, ³ J _{H> H} = 9.02 Hz); 7.62 ppm (H ⁶ , d, J _{H, H} = 1.85 Hz); 6.97 ppm (H ⁴ , dd, ³ J _aH = 8.98 Hz, ⁴ J _a "= 1.83 Hz); 3.20 ppm (4H, t, ³ J _aH = 5.57 Hz, N (CH ₂ ) ₂ ); 2.08 ppm (3H, s, C (= O) CH _3); 1.76 ppm (4H, s, N (CH ₂ CH ₂₎ _2); 1.52 ppm (4H, s, N (CH ₂ CH ₂ CH ₂ ) ₂ ) ;. Step b) N- (5-amino-2-nitrophenyl) azepane

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reacting N- (5-acetylamino-2-nitrophenyl) azepane with hydrochloric acid.

Yield: 19.8 g (95.6% of theory) of yellow crystals

IR: 3460, 3353 cm ^" '(v CH, 3230, 2926, 2855 cm ^" ' (v CH), 1607 cm ^" '(v

C = C), 1550 cm ^'1 (v _as NO ₂ ), 1362 cm ^" ' (v _s NO ₂ ). 'H-NMR: 7.65 ppm (H ³ , d, ³ J _HH = 9.08 Hz ); 6.19 ppm (H ⁶ , d, ⁴ J _aH = 1.95 Hz); 6.16 ppm (2H, s, NH ₂ ); 6.05 ppm (H ⁴ , dd, ³ J _a „= 9.02 Hz, J _H. "= 1.85 Hz); 3.18 ppm (4H, t, ³ J _aH = 5.48 Hz, N (CH ₂ ) ₂ ); 1.72 ppm (4H, s , N (CH ₂ CH ₂ ) ₂ ); 1.53 ppm (4H, s, N (CH ₂ CH ₂ CH ₂ ) ₂ ) ;.

1.3.12. Preparation of N- (5-amino-2-nitrophenyl) morpholine stage a) N- (5-acetylamino-2-nitrophenyl) morpholine

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetaniIid with morpholine.

Yield: 25.6 g (96.5% of theory) of yellow crystals

IR: 3291 cm ^" '(v CH, 2968, 2836 cm ^" ' (v CH), 1698 cm ^" '(v C = O), 1612 cm ^"

'(v C = C), 1550 cm ^" ' (v ,, NO ₂ ), 1331 cm ^'1 (v _s NO ₂ ).' H-NMR: 10.54 ppm (1H, s, NHAc); 8, 1 ppm (H ³ , d, ³ J _H = 9.02 Hz); 7.71 ppm (H ⁶ , d, ⁴ J _HH = 2.08 Hz); 7.48 ppm (H \ dd, ³ J _HH = 8.97 Hz, ⁴ J _H = 2.08 Hz); 3.9 ppm (4H, t, ³ J _aH = 4.54 Hz, N (CH ₂ CH ₂ O) ₂ ); 3.13 ppm ( 4H, t, ³ J _HH = 4.56

Hz, N (CH ₂ CH ₂ O) ₂ ); 2.27 ppm (3H, s, C (= O) CH ₃ ) ;. Step b) N- (5-amino-2-nitrophenyl) morpholine

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyl) mo hoiin with hydrochloric acid. Yield: 19.2 g (95.6% of theory) of yellow crystals

Melting point: (red oil) IR: 3466, 3320, 3220 cm ^" '(v CHJ, 2970, 2867 cm ^{" 1} (v CH), 1606 cm ^{' 1} (v

C = C), 1572 cm ^" '(v ^ NO,), 1344 cm ^" ' (v _s NO ₂ ). 'H NMR: 7.88 ppm (H ³ , d, ³ J _H = 8.63 Hz); 6.51 ppm (2H, s, NH ₂ ); 6.22 ppm (H ⁴ H ⁶ , m); 3.73 ppm (4H, t, ³ J _aH = 4.44 Hz, N (CH ₂ CH ₂ O) ₂ ); 2.92 ppm (4H, t, ³ J _aH

= 4.47 Hz, N (CH ₂ CH ₂ O) ₂ ).

1.3.13. Preparation of N- (5-amino-2-nitrophenyl) piperazine stage a) N- (5-acetylamino-2-nitrophenyl) piperazine

Stage a) was carried out analogously to Example 1.3.3. Step a) by reacting 3-chloro-4-nitroacetanilide with piperazine. Yield: 21.5 g (81% of theory) of yellow crystals z9

IR 3435 cm ^" '(v CHJ, 3039, 2920, 2853 cm ^{' 1} (v CH), 1695 cm ^" '(v C = O), 1615 cm ^" ' (v C = C), 1558 cm ^" '(v .. NO ₂ ), 1366 cm ^" '( _vs NO ₂ ).

'H NMR: 10.32 ppm (1H, s, NHAc); 7.86 ppm (H \ d, ³ J _HH = 9.01 Hz); 7.51 ppm

(H ⁶ , d, ⁴ J _H = 1.93 Hz); 7.25 ppm (H \ dd, ³ J _H = 8.99 Hz, ⁴ J _HH = 1.97 Hz); 2.86 ppm (4H, t, ³ J _H = 5.65 Hz, N (CH ₂ CH ₂ NH) ₂ ); 2.82 ppm (4H, t, ³ J _aH = 5.67 Hz, N (CH ₂ CH ₂ NH) ₂ ); 2.09 ppm (3H, s, C (= O) CH ₃ ) ;.

Step b) N- (5-amino-2-nitrophenyl) piperazine

The preparation in stage b) was carried out analogously to example 1.3.3. Step b) by reaction of N- (5-acetylamino-2-nitrophenyl) piperazine with hydrochloric acid.

Yield: 14.6 g (93.8% of theory) of yellow crystals

IR: 341 1, 3317, 3217 cm ^" '(v CHJ, 2962, 2837 cm ^{' 1} (v CH), 1608 cm ^" '(v

C = C) 1567 cm ^" '(v .. NO _2), 1349 ^cm"' (v _s NO _2).

'H NMR: 7.88 ppm (H ³ , d, ³ J _H = 9.66 Hz); 6.59 ppm (2H, s, NH ₂ ); 6.26 ppm (H \ dd, ³ J _H = 9.56 Hz, ⁴ J „= 2.18 Hz,); 6.25 ppm (H ⁶ , d, ⁴ J _H = 2.07 Hz,); 5.2 ppm (1H, s, NH); 3.02 ppm (8H, s, N (CH ₂ CH ₂ NH) _2).

1.4. Further compounds of the general formula (I) according to the invention Further compounds of the general formula (I) according to the invention are listed in Table 1 below.

Table 1: Compounds of the general formula (I) according to the invention, their absorption maximum and their color.

Rl R2 R3 R4 R5 R6 R7 λ mav color

1 HHHH CH ₃ HH 444 yellow

2 H H H H H CH H 443 yellow

3 HHHHHH CH ₃ 440 yellow

4 HHHH OCH ₃ HH 456 yellow

5 HHHHH OCH ₃ H 427 yellow

6 HHHHHH OCH ₃ 444 yellow

7 H CH ₃ H CH ₃ FHH 452 yellow 2. Colorings:)

2.1. Cream-based colorants:

Dye according to formula (I) x, x g

Sodium lauryl sulfate (70%) 2.5 g

Oleic acid 1.0 g

Sodium sulfite, anhydrous 0.6 g

Cetyl stearyl alcohol 12.0 g

Myristyl alcohol 6.0 g

Propylene glycol 1.0 g

Ammonia, 25% 10.0 g

Oxidation dye precursors y, y g

Water ad 100 g

2.2. Compounds according to formula (I)

(1-1) N, N, -Dimethyl-3-amino-4-nitro-aniline (1-2) N- (3-amino-4-nitrophenyl) morpholine (1-3) N- (5-amino -2-nitrophenyl) pyrrolidine (I-4) N- (5-amino-2-nitrophenyl) piperidine (I-5) N- (5-amino-2-nitrophenyl) moφholin

2.3. Oxidation dye products

- Developer component: (E-l) 2,5-diaminotoluene sulfate

- Coupler component:

(K-l) 2-amino-4-hydroxyethylamino anisole sulfate (HC Blau AC)

2.4. method

50 g of the colorant (in the case of the formulation with the Oxidationsfarbstoffvoφrodukte shortly before use with 50 g H ₂ O ₂ solution (6% in water) mixed) with a brush on 100% gray hair (4 g of colorant per g Hair). After a contact time of 30 minutes at room temperature, the colorant was rinsed off and the hair was dried. O 98/01105

30

2.5. Results

The results of the colorations are summarized in the following table:

Example dye oxidation dye color according to formula (I) voφrodukte

1 2.23 g 1-1 - evenly light orange

2 2.21 g 1-2 - evenly orange

3 2.21 g 1-2 0.27 g E-1

+ 0.79 g K-l evenly wheat blonde

4 2.07 g 1-3 - evenly light orange

5 2.21 g 1-4 - evenly light yellow

6 2.23 g 1-5 - evenly yellow

7 2.23 g 1-5 0.27 g E-l even light violet

+ 0.79 g K-l with blue reflex

Claims

Patent claims

1. Agent for dyeing keratin fibers, characterized in that a 4-nitroaniline derivative of the formula (I) as direct dye;

in which R ,, R ₂ , R ₃ and R ₄ independently of one another represent a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfalkyl, Piperidinoalkyl, Moφholinoalkyl- or a phenyl radical, which is optionally substituted in para position with an amino group, these alkyl or alkoxy groups having one to four carbon atoms, with the proviso that not all four substituents R "R ₂ , R ₃ and R ₄ simultaneously represent hydrogen, and the groups -NR, R ₂ and / or -NR ₃ R _{4 can} also represent an aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, Moφholin-, Thiomoφholin - or a piperazine ring which can also carry a further substituent R ⁸ on the nitrogen atom, where R _{8 is} a hydrogen atom, a (C, -C ₄ ) -alkyl, a hydroxy- (C ₂ -C ₃ ) -alkyl- , a (C, -C ₄ ) alkoxy- (C ₂ -C ₃ ) alkyl-, an amino- (C ₂ -C ₃ ) alkyl- or a 2,3- Is dihydroxypropyl group, and R ₅ , Rg and R ₇ independently of one another for a hydrogen atom, a halogen atom, a (C, -C ₄ ) alkyl, a (C, -C ₄ ) alkoxy radical, a carboxy, sulfo or a (C ₂ -C ₄ ) hydroxyalkyl radical, or a physiologically compatible salt of these compounds with an inorganic or organic acid is present.

Agent according to claim 1, characterized in that one of the groups -NR, R ₂ or -NR ₃ N ₄ for an aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, Moφholin-, Thiomoφholin- or one Piperazine ring, which can also carry a further substituent R ₈ on the nitrogen atom, where R _{8 is} a hydrogen atom, a (C, -C ₄ ) alkyl, a hydroxy (C ₂ -C ₃ ) alkyl, a ( Is C, -C ₄ ) alkoxy- (C ₂ -C ₃ ) alkyl, an amino (C ₂ -C ₃ ) alkyl or a 2,3-dihydroxypropyl group.

Third

2--

3. Agent according to one of claims 1 or 2, characterized in that the compound of formula (I) in amounts of 0.001 to 10 wt .-%, in particular from 0.1 to 5 wt .-%, based on the total agent , is included.

4. Agent according to one of claims 1 to 3, characterized in that it contains a further substantive dye.

5. Agent according to one of claims 1 to 4, characterized in that it further contains an oxidation dye Voφrodukt of the developer type.

6. Composition according to one of claims 1 to 5, characterized in that it further contains an oxidation dye Voφrodukt of the coupler type.

7. Use of 4-nitroanilines of the general formula (I) according to Claim 1 or 2 for dyeing keratin fibers.