DE19728336A1 - Hair dyeing composition containing direct 2-nitro-aniline dye - Google Patents

Abstract

Agents for dyeing keratin fibres contain a direct 2-nitroaniline dye of formula (I) or its salt with an (in)organic acid. R1 - R4 = H, alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, 'sulphalkyl', piperidinoalkyl, morpholinoalkyl, phenyl or p-aminophenyl, where alkyl moieties have 1-4C and R1 - R4 are not all H; or -NR1R2 and -NR3R4 = aziridino, azetidino, pyrrolidino, piperidino, azepino, azocino, morpholino, thiomorpholino or piperazino (optionally N-substituted by H, 1-4C alkyl, 2-3C hydroxyalkyl, (1-4C) alkoxy-(2-3C) alkyl, 2-3C aminoalkyl or 2,3-dihydroxypropyl; R5 - R7 = H, halogen, 1-4C alkyl, 1-4C alkoxy, carboxy, sulpho or 2-4C hydroxyalkyl. The use of (I) for dyeing keratin fibres is also claimed.

Description

The invention relates to agents for dyeing keratin fibers with special 2-nitroaniline Derivatives as substantive dyes.

For dyeing keratin fibers in addition to so-called oxidation dyes and di Rectifying dyes used. In contrast to the oxidation dyes in which The dye precursors penetrate into the hair and only there under the influence of Oxi dationsmitteln form the actual dyes, these dyes are able to hair to dye directly. Under the technical application conditions (deep dyeing temp temperature and short dyeing time) give intense colors with good fastness properties. This dif base the dyes in the fiber during the dyeing process. As a directing Dyes for dyeing keratin fibers are usually nitrophenylenediamines, Nitroaminophenols, anthraquinones or indophenols used. such direct dyes to achieve a variety of hues, hereinafter referred to as Direct drawers, play an important role in hair coloring. These Dyes must in coloring the desired color with sufficient intensity give the obtained colors must have good light and acid fastness, and Under the wearing conditions they must not lead to color shifts of the original Nuance tend. Furthermore, they should be dermatologically and toxicologically safe.  

There are already a large number of direct drawers for dyeing keratin fibers known. Red and yellow substantive dyes are, for example, in DE-AS 21 57 844 and DE-OS 33 23 207 discloses. However, these have some disadvantages. That's how it is Solubility of these compounds, which is a significant for proper coloration Role plays, very low. The luminosity and color intensity of the colors obtained are also not enough. Further substantive dyes based on nitroaniline are known from GB 1 206491 and Chemical Abstracts 85: 95803f.

There is thus a constant need for new direct hair dyes, the in terms of their light fastness, wash fastness and color depth, but also in terms of their toxicological and dermatological properties to ever higher requirements have to suffice. New direct drawers 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 novel compounds to provide the direct dyes to be addressed in fulfill special requirements.

Surprisingly, it has now been found that the be in the present invention be compounds of the general formula (I) described these claims particularly well fulfill.

The present invention therefore relates to agents for dyeing keratin fibers, the direct-acting dye is a 2-nitroaniline derivative of the general formula (I),

in which R₁, R₂, R₃ and R₄ are independently
a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, Me sylaminoalkyl-, acetylaminoalkyl, Ureidoalkyl-, Carbalkoxyaminoalkyl-, sulfalkyl, Pi peridinoalkyl-, Morpholinoalkyl- or a phenyl radical, optionally in para-posi tion with an amino group is substituted, these alkyl or alkoxy groups having one to four carbon atoms, with the proviso that not all four substituents R₁, R₂, R₃ and R₄ are simultaneously hydrogen,
and the groups -NR₁R₂ and / or -NR₃R₄ can also be an aziridine, Azeti din-, pyrrolidine, piperidine, azepane, azocine, morpholine, thiomorpholine or a piperazine ring, on the nitrogen atom and a R weiteren is a hydrogen atom, a (C₁-C₄) alkyl, a hydroxy (C₂-C₃) alkyl, a (C₁-C₄) alkoxy (C₂-C₃) alkyl, is an amino (C₂-C₃) alkyl or a 2,3-dihydroxypropyl group,
and R₅, R₆ and R₇ independently represent a hydrogen atom, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, carboxy, sulfo or (C₂-C₄) hydroxyalkyl, or the like physiologically acceptable salt of these compounds with an inorganic or organic acid.

Among keratin fibers are furs, wool, feathers and especially human hair to understand. Although the colorants of the invention are primarily for dyeing Keratin fibers are suitable, is in principle a use also on others Areas nothing contrary.

The preparation of the compounds of formula (I) can by known methods he consequences. For this purpose, reference is expressly made to the comments in the examples section.

Particularly excellent coloring properties show compounds according to Formula (I) wherein the group -NR₁R₂ is an aziridine, azetidine, pyrrolidine, pipe ridine, azepane, azocine, morpholine, thiomorpholine or a piperazine ring, which on  Nitrogen atom can also carry another substituent R₈, where R₈ is a water 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 is.

Preferred substituents R₁ to R₇ are, as far as in the context of the general formula (I) permissible, hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-aminoethyl and 2,3-dihy droxypropylgruppen.

The compounds of the formula (I) can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. B. the Hydrochlorides, sulfates and hydrobromides. Further, suitable for salt formation Neten acids are phosphoric acid and acetic acid, propionic acid, lactic acid and Citric acid. The statements on the compounds according to Therefore, formula (I) always includes these salts.

The hair colorants according to the invention contain the compounds of the formula (I) preferably in an amount of 0.001 to 10 wt .-%, preferably 0.1 to 5 wt .-%, in each case based on the entire colorant. Under the "total colorant" is here and in the following understood the means provided to the user becomes. This agent may, depending on the formulation form, either directly or, if that Agent additionally contains oxidation dye precursors, after mixing with water or z. As an aqueous solution of an oxidizing agent applied to the hair become.

According to a first preferred embodiment, the means for dyeing Keratin fibers as substantive dye a 2-nitroaniline derivative of the general Formula (I),

in which R₁, R₂, R₃ and R₄ independently of one another represent a hydrogen atom, an alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfalkyl, piperidinoalkyl, morpholinoalkyl or phenyl radical which is optionally present in substituted para-position with an amino group, said alkyl or alkoxy groups having one to four carbon atoms, with the proviso that not all four substituents R₁, R₂, R₃ and R₄ are simultaneously hydrogen,
and the groups -NR₁R₂ and / or -NR₃R₄ can also be an aziridine, Azeti din-, pyrrolidine, piperidine, azepane, azocine, morpholine, thiomorpholine or a piperazine ring, on the nitrogen atom and a R weiteren is a hydrogen atom, a (C₁-C₄) alkyl, a hydroxy (C₂-C₃) alkyl, a (C₁-C₄) alkoxy (C₂-C₃) alkyl is an amino (C₂-C₃) alkyl or a 2,3-dihydroxy propyl group, with the proviso that in the event that only one of the two groups -NR₁R₂ or -NR₃R₄ is such a ring system,

• - The other substituents R₃ and R₄ or R₁ and R₂ independently may also be hydrogen, a (C₁-C₄) -alkyl or a (C₂-C₃) -hydroxyalkyl Group and
• at least one of the substituents R₅, R₆ or R₇ does not stand for hydrogen,

and R₅, R₆ and R₇ independently represent a hydrogen atom, a (C₁-C₄) - Alkyl, a (C₁-C₄) alkoxy, a carboxy, sulfo or a (C₂-C₄) - Hydroxyalkylrest, or a physiologically acceptable salt of these compounds with an inorganic or organic acid.  

According to this first preferred embodiment, the inventive Means only the compounds of formula (I) as a dye component.

However, the number of accessible shades is significantly increased when the agent next to the compounds of formula (I) nor a further substantive dye or contains an oxidation dye precursor.

According to a second, likewise preferred embodiment, the inventive Colorant in addition to the compounds corresponding to formula (I) according to claim 1, optionally in addition to oxidation dye precursors, for the modification of Farbnu additionally at least one further substantive dye, eg. B. from the Grup pe of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols. Preferred substantive dyes are those under international designations 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, picric acid and Rodol 9 R known compounds as well as 4-amino-2 nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, (N-2,3- Dihydroxypropyl-2-nitro-4-trifluoromethyl) aminobenzene and 4-N-ethyl-1,4-bis (2'- hydroxyethylamino) -2-nitrobenzene hydrochloride. The agents according to the invention This embodiment preferably contains the further substantive dye in an amount of 0.01 to 20 wt .-%, based on the total colorant.

Furthermore, the colorants of the invention may also occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alcano root included.

According to a third, likewise preferred embodiment, the erfindungsge Mäß means in addition to the compounds according to formula (I) according to claim 1 and  if desired, substantive dyes and an oxidation dye precursor coupler type, nor at least one developer-type oxidation dye precursor.

Developer components preferred according to the invention are p-phenylenediamine, p-toluene lendiamine, p-aminophenol, 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-di aminobenzene, N, N-bis (2-hydroxy-ethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) - ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazolone-5,4-amino-3-methylphenol, 2- Methylamino-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triamino pyrimidine, 4-hydroxy-2,5,6, -triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-Dimethylamino-4,5,6-triaminopyrimidine and 2-hydroxyethylaminomethyl-4-amino phenol.

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

Of course, this embodiment also includes the use of multiple Ent wicklerkomponenten. According to preferred coupler combinations 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 erfindungsge Mäß means therefore in addition to the compounds according to formula (I) according to claim 1 and, if desired, further substantive dyes and oxidation dye prepro of the developer type, at least one oxidation dye precursor of Intermediate type.  

Preferred coupler components 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, 1-phenyl-3- methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-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-dihydroxy-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.

Particularly preferred according to the invention are 1,7-dihydroxynaphthalene, m-aminophenol, 2-methylresorcinol, 4-amino-2-hydroxytoluene, 2-amino-4-hydroxyethylamino-anisole and 2,4-diaminophenoxyethanol.

Of course, this embodiment also includes the use of multiple Kupp lerkomponenten. According to preferred coupler combinations 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-hy droxypyridin
• 2-methylresorcinol, m-aminoaniline, 2-hydroxy-4-aminotoluene, 2-amino-3-hydroxypy ridin.

Usually, developer components and coupler components become approximately used molar amounts to each other. If the molar use as purpose has been found to be moderate, so there is a certain excess of individual oxidation dye precursors not disadvantageous, so that developer components and Coupler components preferably in a molar ratio of 1: 0.5 to 1: 2 in  Colorants may be included. The total amount of oxidation dye precursors is usually at most 20 wt .-%, based on the total mean.

It is not necessary that the direct or optional contained Dyes or the optionally contained oxidation dye precursors each represent uniform connections. Rather, in the hair of the invention Colorants, due to the production process for the individual dyes, in Subordinate quantities may contain other components, as far as these are not the staining result adversely affect or other reasons, eg. B. toxicological, must be excluded.

Conventional packaging forms for the oxidation colorants according to the invention are Means based on water or nonaqueous solvents and powders.

According to a preferred embodiment for the preparation of the dye according to the invention At least the oxidation dye precursors are converted into a suitable hydrous material Carrier incorporated. For the purpose of hair coloring such carrier z. Creams, Emulsions, gels or surfactant-containing foaming solutions, eg. Shampoos, Foam aerosols or other preparations intended for use on the hair are suitable. The colorants according to the invention are preferably adjusted to a pH Value of 6.5 to 11.5, especially 9 to 10, adjusted.

Furthermore, the colorants of the invention may be all in such preparations be knew active ingredients, additives and excipients included. In many cases, the included Colorant at least one surfactant, where in principle both anionic and zwitterionic, anipholytic, nonionic and cationic surfactants are suitable. In In many cases, however, it has proven to be advantageous to use anionic surfactants, select zwitterionic or nonionic surfactants. Anionic surfactants can be particularly preferred.  

Suitable anionic surfactants in preparations according to the invention are all suitable for the United use on the human body of suitable anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of about 10 to 22 carbon atoms. In addition, in the molecule glycol or poly glycol ether groups, ether, amide and hydroxyl groups and, as a rule, also Be included ester groups. Examples of suitable anionic surfactants are, in each case in Form of sodium, potassium and ammonium as well as the mono-, di- and Trialkanolammonium salts having 2 or 3 C atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 22 carbon atoms (soaps),
• - Ethercarbonsäuren the formula RO- (CH₂-CH₂O) _x -CH₂-COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• - Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
• - alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (-CH₂-CH₂O) _x -SO₃ H, in which R is a preferably linear alkyl group having 10 to 18 carbon atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A 37 25 030,
• - Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylenepropylene glycol ether according to DE-A 37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 doublebin according to DE-A 39 26 344,  
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide Represent fatty alcohols having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ethers carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and in particular unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or SO₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinate, example, the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethyl ammoniumglycinate, for example, the Kokosacylaminopropyl-dimethyl-ammonium 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 hydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean such surface-active compounds in addition to a C8-C18 alkyl or acyl group in the molecule at least one free Amino group and at least one -COOH or -SO₃H group and to off formation of internal salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyl iminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N- Alkyl sarcosines, 2-Alkylaminopropionsäuren and Alkylaminoessigsäuren each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and the C12-18 acyl sarcosine.  

Nonionic surfactants contain as hydrophilic group z. B. a polyol group, a Po lyalkylenglykolethergruppe or a combination of polyol and polyglycol ether group. Such compounds are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 mol Propylene oxide to linear fatty alcohols with 8 to 22 C-atoms, to fatty acids with 12 to 22 C atoms and to alkylphenols having 8 to 15 C atoms in the alkyl group,
• C12-C22 fatty acid mono- and diesters of addition products of 1 to 30 mol Ethylene oxide with glycerol,
• C8-C22 alkyl mono- and oligoglycosides and their ethoxylated analogs,
• - Addition products of 5 to 60 moles of ethylene oxide to castor oil and hardened castor oil,
• Adducts of ethylene oxide with sorbitan fatty acid esters,
• - Addition products of ethylene oxide to fatty acid alkanolamides.

Examples of the usable in the hair treatment compositions according to the invention katio Nischen Tenside are in particular quaternary ammonium compounds. Preferred are Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldi-methylammoni Umchloride and Trialkylmethylammoniumchloride, z. B. cetyltrimethylammonium chloride chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldi methylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylme methylammonium. Further cationic surfactants which can be used according to the invention represent the quaternized protein hydrolysates.

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

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect especially by their good biodegradability.

Also very readily biodegradable are quaternary ester compounds, so-called "Esterquats", such as the dialkylammoni sold under the trademark Stepantex® ummethosulfate and methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfate.

An example of a cationic surfactant employable quaternary sugar derivative the commercial product Glucquat®100, according to CTFA nomenclature a "Lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride ".

The compounds used as surfactants with alkyl groups may be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one Substance mixtures with different, dependent on the particular raw alkyl chain ten lengths.

In the case of the surfactants, the addition products of ethylene oxide and / or propylene oxide Fatty alcohols or derivatives of these addition products, both Pro products with a "normal" distribution of homologs as well as those with a narrower Homolog distribution can be used. Under "normal" homolog distribution this understood mixtures of homologues, which in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrow homolog distributions in contrast, obtained when, for example, hydrotalcites, alkaline earth metal salts of Ethercarbonsäuren, alkaline earth metal oxides, hydroxides or alkoxides as catalysts  be used. The use of products with restricted Homolog distribution may be preferred.

Other active ingredients, auxiliaries and additives are, for example

• nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copoly mers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysi Loxane,
• - cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide Dimethyldiallylammonium chloride copolymers, quaternized with diethyl sulfate Dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• zwitterionic and amphoteric polymers such as acrylamidopropyl tri methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.Butylaminoethylmethacrylat / 2 Hydroxypropylmethacryl-at-copoly mers
• anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextrans, cel lulose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, Clays such as As bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol hol,
• - structurants such as glucose, maleic acid and lactic acid,  
• Hair conditioning compounds such as phospholipids, for example soya lecithin, Egg lecithin and cephalins, as well as silicone oils,
• - Protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, Glycerine and diethylene glycol,
• Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine,
• Alkalizing agents such as ammonia, monoethanolamine, 2-amino-2- methylpropanol and 2-amino-2-methyl-1,3-propanediol.
• - other substances for adjusting the pH,
• - Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - sunscreen,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as spermaceti, 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, Carbo nate, bicarbonates, guanidines, ureas and primary, secondary and ter tiary phosphates,
• Opacifiers such as latex,
• Pearlescing agents such as ethylene glycol mono- and distearate,
• - Propellant such as propane-butane mixtures, N₂O, dimethyl ether, CO₂ and Air,
• - antioxidants.

The constituents of the water-containing carrier are used for the preparation of the inventive ßen colorants used in customary amounts for this purpose; z. B. become emulsifiers medium in concentrations of 0.5 to 30 wt .-% and thickener in Konzentratio NEN from 0.1 to 25 wt .-% of the total colorant used.

If the agents according to the invention contain oxidation dye precursors, the oxidative development of the staining principle with atmospheric oxygen or one in the Containing or added directly before the application of oxidation done medium.

According to a first embodiment, a chemical oxidizing agent is used. This is particularly advantageous in such cases, when in addition to the coloring one Whitening effect on human hair is desired. Come as an oxidizing agent in particular hydrogen peroxide or its addition products of urea, Melamine or alkali borate in question. According to a particularly preferred variant of this Embodiment, the colorant of the invention immediately before Application with the preparation of the oxidizing agent, in particular an aqueous H₂O₂ solution, mixed. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 10. Particularly preferred is the Application of hair dye in a weak alkaline environment. The application Temperatures can range between 15 and 40 ° C. After a Einwir The hair dye is rinsed by rinsing it for about 30 minutes removing coloring hair. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, for. As a dyeing shampoo was used.

Especially with hair that is difficult to dye, the preparation with the oxidation color Stoffvorprodukten without prior mixing with the oxidation component on the Hair will be applied. After an exposure time of 20 to 30 minutes then - optionally after an intermediate rinse - the oxidation component applied.  

After a further exposure time of 10 to 20 minutes is then rinsed and if desired nachshampooniert.

According to a second embodiment, the coloration is carried out with atmospheric oxygen. there For example, it is advantageous to add an oxidation catalyst to the colorant according to the invention give. Suitable oxidation catalysts are metal salts or metal complexes, wherein Transition metals may be preferred. Preferred are copper, manganese, Cobalt, selenium, molybdenum, bismuth and ruthenium compounds. Copper (II) chloride, sulfate and acetate may be preferred oxidation catalysts. As metal complexes the complexes with ammonia, ethylenediamine, phenanthroline, triphenylphosphine, 1,2-diphenylphosphinoethane, 1,3-diphenylphosphinopropane or amino acids be preferred. Of course, it is also possible to have more than one agent Use oxidation catalysts. With regard to the preparation of suitable catalysts is expressly based on the corresponding disclosure in EP 0 709 365 A1 (page 4, drawing len 19 to 42), to which reference is expressly made.

Furthermore, it is possible to carry out the oxidation by means of enzymes. there Both the enzymes can be used to produce oxidizing per-compounds used as well as to enhance the effect of small amounts existing oxidizing agent. An example of an enzymatic process is the The effect of small amounts (eg 1% and less, based on the total agent) to amplify hydrogen peroxide by peroxidases.

Another object of the invention is the use of 2-nitroanilines of the general my formula (I) according to claim 1 for coloring keratinic fibers.

The compounds of the general formula (I) can be obtained by reduction of the 2-nitro group into compounds of general formula (Ia), in place of the 2-Ni trogruppe a 2-amino group is present

and R₁ to R₇ have the same meaning as in the general formula (I). In the Ver Compounds of general formula (Ia), the 2-amino group by alkylation or Oxalkylation into a substituted 2-amino group in the general formula (Ib) be led

whereby compounds of general formula (Ib) are obtained, in which R₁ to R₇ the have the meaning given for the general formula (I) and R₁₁ and R₁₂ independently each other is a hydrogen atom, a (C₁-C₄) alkyl, a hydroxy (C₂-C₃) alkyl, a Alkoxy (C₂-C₃) alkyl, an amino (C₂-C₃) alkyl or a 2,3-dihydroxypropyl group can represent.

These compounds are especially oxidation dye precursors excellent dyeing properties, the same time coupler and Developer properties have.  

Examples 1. General manufacturing process

Compounds of the general formula (I) according to the invention, in which R₅, R₆ and R₇ Are hydrogen atoms can be prepared by reacting 2-nitro-4-aminohalogen benzenes of the general formula (II) in which X = fluorine, chlorine, bromine or iodine, with Amines of the general formula (III), wherein R₁ and R₂ are those indicated above Have meaning in alkaline reaction medium, optionally with the addition of Phase transfer catalysts for 2-nitro-4-aminoanilines of the general formula (I) be implemented. This reaction may optionally be carried out in an autoclave Pressure occurs when the boiling point of the amine is lower than the reaction temperature or the revenue is otherwise incomplete.

The compounds of general formula (III) are common chemical precursors and can be purchased. Suitable phase transfer catalysts are, for example Example methyl or benzyl tri (C₆-C₈) alkylammonium chloride.

For the alkoxylation are the compounds of general formula (I), for the R₃ and R₄ = hydrogen, in an inert solvent with chloroformic acid-2 Chloroethyl ester (R₉ = CH₂CH₂Cl) or chloroformate 3-chloropropyl (IV) (R₉ = CH₂CH₂CH₂Cl) in compounds of the formula (V)

transferred. The intermediates of formula (V) are labeled thereon with strong bases, e.g. B. Sodium or potassium hydroxide, to compounds of general formula (VI) implemented, in which

R₁₀ = CH₂CH₂OH or CH₂CH₂CH₂OH, with known alkylation or Oxalkylating agents to give products of general formula (I), wherein R₁ to R₄ have the meaning already indicated, and this optionally with an anorgani or organic acid in its salt.

The first step of these processes is principally the replacement of a halo substituent against an amine substituent on the phenyl ring. In the known methods is usually worked with an amine excess of about 40-80%; the products are obtained in yields of about 90% and with a purity of 95-96%.  

Surprisingly, it has now been found that higher yields at the same or better purity and faster conversion when the amine excess is 30% and less, especially 5 to 10 mol%, based on the amounts of the Compound according to formula (II). It is also preferable to have the reaction in one to carry out organic solvents. The reaction is preferably under a Pressure of 1 to 15 bar, in particular from 1 to 8 bar and most preferably from 1 up to 2.5 bar.

Substituted compounds of the general formula (II) are obtainable by unsubstitu ierte compounds of general formula (II), for the R₃ = R₄ = hydrogen, al alkylated or alkoxylated; This is done by putting these compounds in one inert solvent with dialkyl sulfate, alkyl halide or alkylene oxides or by the rearrangement of carbamates of the general formula (V) prepared therefrom, according to known methods, and subsequent treatment with the aforementioned Alkylating agents.

As phase transfer catalysts, for example, methyl or benzyl-tri (C₆- C₈) alkylammonium chlorides or tetraphenylphosphinium chloride are used.

Salt formation, for example, hydrochloric acid, sulfuric acid as inorganic acids or phosphoric acid and as organic acids acetic acid, propionic acid, lactic acid or Citric acid suitable.

1.2. Preparation of Specific Compounds of Formula (I)

The compounds prepared were by IR and IR (KBr-Preßling) and / or 1 H-NMR spectra (in D₆-DMSO) characterized. As far as the spectra specified here only the very strong and strong bands are listed in the IR spectra. at the data for the 1 H-NMR spectra mean singlet, d doublet, dd doublet from  Doublet, t triplet, q quartet, qi quintet, m multiplet, ³J or ⁴J the couplings above three or four bonds as well as H³, H³ and H⁶ the hydrogen atoms in position 3, 5 or 6 of the benzene ring.

1.2. 1. Preparation of 4-amino-2-nitro-N, N-dimethylaniline

In 250 ml of 1,2-dimethoxyethane, 62.5 g (0.4 mol) of 4-fluoro-3-nitraniline, 45.1 g (0.4 mol, 40% sol.) Of dimethylamine and 21.2 g ( 0.2 mol) of sodium carbonate submitted. The mixture was heated and refluxed until the reaction was complete, then each 1 g activated carbon and celite was added, stirred for about 30 minutes and filtered. The product was freed from the solvent using a rotary evaporator and the resulting oil was further processed.
Yield: 62.8 g (86.6% of theory)
Melting point: (oil)
IR: 3373 cm ^-1 (ν CH _Ar ), 3227, 2946, 2870, 2792 cm ^-1 (ν CH), 1631 cm ^-1 (ν C = C), 1564, 1525 cm ^-1 (ν _as NO₂), 1353, 1293 cm ^-1 (ν _s NO₂).
1 H-NMR: 7.10 ppm (H, d, 3 _{H, H} = 8.77 Hz); 6.94 ppm (H3, d, ⁴JH _{, H} = 2.64 Hz); 6.83 ppm (H⁵, dd, ³J _{H, H} = 8.77 Hz, ⁴J _{H, H} = 2.70 Hz); 5.29 ppm (2H, s, N H ₂); 2.59 ppm (6H, s, N (C H ₃) ₂).

1.2.2. Preparation of 4- (2-hydroxyethylamino) -2-nitro-N, N-dimethylaniline Stage a) 4-amino-2-nitro-N, N-dimethylaniline

The implementation of stage a) is carried out as in Example 1.2.1. specified by conversion of 4-fluoro-3-nitraniline with dimethylaniline.

Stage b) 4- (2-Chloroethoxycarbonylamino) -2-nitro-N, N-dimethylaniline

In 100 ml of 1,2-dimethoxyethane, 28.5 g (160 mmol) of 4-amino-2-nitro-N, N-dime thylaniline and 9 g (80 mmol) of calcium carbonate submitted. To this solution was dripped At room temperature, 22.5 g (160 mmol) of 2-chloroethyl chloroformate and The mixture was stirred until the conversion was complete. Then it became more concentrated Hydrochloric acid adjusted the pH to 3-4 and added 100 g of ice / water mixture.  

The precipitated product was filtered off and washed twice with 100 ml of water.
Yield: 25.5 g (59.1% of theory)
Melting point: 178-180 ° C
IR: 3424 cm ^-1 (ν CH _Ar ), 3177, 3032 cm ^-1 (ν CH), 1727 cm ^-1 (ν C = O), 1607 cm ^-1 (C = C), 1544 cm ^-1 (ν _as NO₂ ), 1322 cm ^-1 (ν _s NO₂), 1227 cm ^-1 (ν OC).
1 H-NMR: 8.03 ppm (H³, d, ⁴J _{H, H} = 2.15 Hz); 7.62 ppm (H⁵, dd, ³J _{H, H} = 9.06 Hz, ⁴J _{H, H} = 2.55 Hz); 7.35 ppm (H⁶, d, ³J _{H, H} = 9.11 Hz); 4.36 ppm (2H, q, C (O) OC H ₂); 3.89 ppm (2H, q, CH₂Cl); 2.83 ppm (6H, s, N (C H ₃) ₂).

Step c) 4- (2-Hydroxyethylamino) -2-nitro-N, N-dimethylaniline

In 100 ml of ethanol were placed 23.0 g (80 mmol) of 4- (2-chloroethoxycarbonylamino) -2-nitro-N, N-dimethylaniline. To this solution was added dropwise at room temperature 33 g (412 mmol) of 50% sodium hydroxide solution and the mixture was stirred until the conversion was complete. Then the mixture was heated to about 80 ° C and the solution was filtered. The pH of the filtrate was adjusted to 8 with acetic acid. Then 75 ml of water were added and the ethanol was distilled off until the boiling point reached 99.degree. After the solution had cooled, it was extracted with ethyl acetate, the ester phase dried over sodium sulfate and concentrated in vacuo; after rubbing with a glass rod, the product crystallized, which was filtered off with suction and dried.
Yield: 12.1 g (67.2% of theory)
Melting point: 110 ° C
IR: 3285 cm ^-1 (ν CH _Ar ), 3178 cm ^-1 (ν CH), 1640 cm ^-1 (ν C = O), 1559 cm ^-1 (ν _as NO₂), 1413 cm ^-1 (ν _s NO₂), 810 cm ^-1 (ν CH _oop ).
¹H-NMR: 7.19 ppm (H⁶, d, ³J _{H, H} = 9.60 Hz); 6.855 ppm (H⁵, dd, ³J _{H, H} = 9.64 Hz, ⁴J _{H, H} = 2.87 Hz); 6.854 ppm (H, d, ⁴ J _{H, H} = 2.50 Hz); 6.01 ppm (1H, t, 3 J _{H, H} = 11 Hz, CH₂OH); 3.54 ppm (2H, t, 3 J _{H, H} = 5.81 Hz, NCH₂); 3.07 ppm (2H, q, 3 J _{H, OH} = 11.35 Hz, 3 J _{H, H} = 5.65 Hz, C H ₂OH); 2.59 ppm (6H, s, N (C H ₃) ₂).

1.2.3. Preparation of N- (4-amino-2-nitrophenyl) morpholine

The preparation of the compound was carried out analogously to Example 1.2.1. with morpholine instead of dimethylamine.
Yield: 61.9 g (69.3% of theory)
Melting point: 131-132 ° C
IR: 3479 cm ^-1 (ν CH _Ar ), 3042, 2958, 2857, 2830 cm ^-1 (ν CH), 1626 cm ^-1 (ν C = C), 1515 (ν _as NO₂), 1343 cm -1 (ν _s NO₂).
¹H-NMR: 7.18 ppm (H⁶, d, ³J _{H, H} = 8.66 Hz); 6.88 ppm (H³, d, ⁴ J _{H, H} = 2.44 Hz); 6.80 ppm (H⁵, dd, ³J _{H, H} = 8.59 Hz, ⁴J _{H, H} = 2.43 Hz); 5.46 ppm (2H, s, N H ₂); 3.63 ppm (4H, t, 3 J _{H, H} = 4.66 Hz, OCH₂); 2.79 ppm (4H, t, 3 J _{H, H} = 4.43 Hz, NCH₂).

1.2.4. Preparation of N- [4- (2-hydroxyethylamino) -2-nitrophenyl] morpholine Stage a) N- (4-amino-2-nitrophenyl) morpholine

The compound was as in Example 1.2.1. indicated, produced, however, was of dimethylamine now used morpholine.

Stage b) N- [4- (2-chloroethoxycarbonylamino) -2-nitro-phenyl] morpholine

The conversion to stage b) was carried out analogously to Example 1.2.2. Stage b), but instead of 4-amino-2-nitro-N, N-dimethylaniline now N- (4-amino-2-nitrophenyl) morpholine was used.
Yield: 32.7 g (95.1% of theory)
Melting point: 121-122 ° C
IR: 3304 cm ^-1 (ν CH _Ar ), 3177, 3102 cm ^-1 (ν CH), 1732 cm ^-1 (ν C = O), 1596 cm ^-1 (C = C), 1537 cm ^-1 (ν _as NO₂ ), 1342 cm ^-1 (ν _s NO₂), 1224 cm ^-1 (ν OC).
1 H-NMR: 10.1 ppm (1H, s, NH); 8.01 ppm (H, d, 3 _{H, H} = 2.21 Hz); 7.64 ppm (H⁵, dd, ³J _{H, H} = 8.89 Hz, ⁴J _{H, H} = 2.46 Hz); 7.85 ppm (H 3, d, 3 _{H, H} = 8.94 Hz); 4.38 ppm (2H, t, 3 _{H, H} = 5.16 Hz, C (O) OC H ₂); 3.89 ppm (2H, t, 3 _{H, H} , 5.16 Hz, CH₂Cl); 3.69 ppm (4H, t, 3 J _{H, H} = 4.48 Hz, CH₂OCH₂); 2.92 ppm (4H, t, 3 J _{H, H} = 4.50 Hz, CH₂NCH₂).

Step c) N- [4- (2-hydroxyethylamino) -2-nitrophenyl] morpholine

The implementation of stage c) was carried out analogously to Example 1.2.2. Stage c), but instead of 4- (2-chloroethoxycarbonylamino) -2-nitro-N, N-dimethylaniline, N- [4- (2-chloroethoxycarbonylamino) -2-nitro-phenyl] morpholine was now used.
Yield: 20 g (93.5% of theory)
Melting point: (oil)
IR: 3282 cm ^-1 (ν CH _Ar ), 2941 cm ^-1 (ν CH), 1632 cm ^-1 (ν C = O), 1567 cm ^-1 (ν _as NO₂), 1368 cm ^-1 (ν _s NO₂ ).
1 H-NMR: 8.6 ppm (4H, s, NH / OH); 7.36 ppm (H⁶, d, ³J _{H, H} = 8.63 Hz); 7.21 ppm (H³, d, ⁴ J _{H, H} = 2.19 Hz); 7.10 ppm (H⁵, dd, ³J _{H, H} = 8.59 Hz, ⁴J _{H, H} = 2.19 Hz); 3.84 ppm (4H, t, 3 J _{H, H} = 4.22 Hz, CH₂OCH₂); 3.67 ppm (2H, t, 3 _{H, H} = 5.47 Hz, C H ₂OH); 3.23 ppm (2H, t, ³J _{H, H} = 5.48 Hz, NC H ₂CH₂OH); 2.97 ppm (4H, t, 3 J _{H, H} = 4.06 Hz, CH₂NCH₂).

1.2.5. Preparation of N- (4-amino-2-nitrophenyl) piperidine

The preparation of the compound was carried out analogously to Example 1.2.1. with piperidine instead of dimethylamine.
Yield: 80.6 g (91.1% of theory)
Melting point: 112-113 ° C
IR: 3486, 3389 cm ^-1 (ν CH _Ar ), 2950, 2934, 2848 cm ^-1 (ν CH), 1629 cm ^-1 (ν C = C), 1511 (ν _as NO₂), 1361 cm ^-1 ( ν _s NO₂).
1 H-NMR: 7.12 ppm (H, d, 3 _{H, H} = 8.68 Hz); 6.86 ppm (H3, d, ⁴JH _{, H} = 2.51 Hz); 6.78 ppm (H⁵, dd, ³J _{H, H} = 8.60 Hz, ⁴J _{H, H} = 2.52 Hz); 5.38 ppm (2H, s, N H ₂); 2.75 ppm (4H, t, 3 _{H, H} = 4.66 Hz, NCH 2) 1.54. , , 1.45 ppm (6H, m, NCH₂CH₂CH₂CH₂ ).

1.2.6. Preparation of N- [4- (2-hydroxyethylamino) -2-nitrophenyl] piperidine Stage a) N- (4-amino-2-nitrophenyl) piperidine

The preparation was carried out analogously to Example 1.2.1. with piperidine instead of dimethylamine.

Step b) N- [4- (2-Chloroethoxycarbonylamino) -2-nitrophenyl] piperidine

The implementation of stage b) was carried out analogously to Example 1.2.2. Stage b) by reacting N- (4-amino-2-nitrophenyl) piperidine with 2-chloroethyl chloroformate.
Yield: 31.1 g (94.8% of theory)
Melting point: 74-76 ° C
IR: 3373 cm ^-1 (ν CH _Ar ), 2936, 2853 cm ^-1 (ν CH), 1730 cm ^-1 (ν C = O), 1588 cm ^-1 (C = C), 1532 cm ^-1 (ν _as NO₂), 1307 cm ^-1 (ν _s NO₂), 1224 cm ^-1 (ν OC).
1 H-NMR: 10.0 ppm (1H, s, NH); 7.96 ppm (H⁶, d, ³J _{H, H} = 2.35 Hz); 7.59 ppm (H⁵, dd, ³J _{H, H} = 8.95 Hz, ⁴J _{H, H} = 2.00 Hz); 7.31 ppm (H 3, d, 3 _{H, H} = 8.97 Hz); 4.36 ppm (2H, t, 3 _{H, H} = 5.19 Hz, C (O) OC H ₂); 3.88 ppm (2H, t, 3 J _{H, H} = 5.19 Hz, CH₂Cl); 2.87 ppm (4H, t³J _{H, H} = 5.03 Hz, CH₂NCH₂); 1.59. , , 1.50 ppm (6H, m, CH₂CH₂CH₂).

Step c) N- [4- (2-Hydroxyethylamino) -2-nitrophenyl] piperidine

The implementation of stage c) was carried out analogously to Example 1.2.2. Stage c) by reaction of 4- (2-chloroethoxycarbonylamino-2-nitrophenyl) piperidine with sodium hydroxide solution.
Yield: 17.7 g (83.5% of theory)
Melting point: (oil).

1.2.7. Preparation of N- (4-amino-2-nitrophenyl] pyrrolidine

The preparation of the compound was carried out analogously to Example 1.2.1. with pyrrolidine instead of dimethylamine.
Yield: 61.0 g (73.6% of theory)
Melting point: 84-86 ° C
IR: 3486, 3389 cm ^-1 (ν CH _Ar ), 2950, 2934, 2848 cm ^-1 (ν CH), 1624 cm ^-1 (ν C = C), 1521 (ν _as NO₂), 1364 cm ^-1 ( ν _s NO₂).
1 H-NMR: 6.98 ppm (H 3, d, 3 _{H, H} = 2.28 Hz); 6.87 ppm (H⁵, H⁶, m); 4.92 ppm (2H, s, N H ₂); 3.00 ppm (4H, t, 3 J _{H, H} = 6.49 Hz, NCH₂); 1.85 ppm (6H, m, NCH₂ CH₂CH₂).

1.2.8. Preparation of N- (4-amino-2-nitrophenyl) azepane

The preparation of the compound was carried out analogously to Example 1.2.1. with azepane instead of dimethylamine.
Yield: 37.2 g (39.5% of theory)
Melting point: 72-73.5 ° C
IR: 3467, 3380 cm ^-1 (ν CH _Ar ), 2926, 2853 cm ^-1 (ν CH), 1631 cm ^-1 (ν C = C), 1520 (ν _as NO₂), 1360 cm ^-1 (ν _s NO₂).
1 H-NMR: 7.07 ppm (H⁶, d, 3 J _{H, H} = 8.64 Hz); 6.79 ppm (H⁵, dd, ³J _{H, H} = 6.96 Hz, ³J _{H, H} = 2.59 Hz); 6.75 ppm (H³, d, ⁴ J _{H, H} = 2.68 Hz); 5.24 ppm (2H, s, N H ₂); 3.00 ppm (4H, t, 3 J _{H, H} = 5.49 Hz, NCH₂); 1.62. , , 1.56 ppm (8H, m, NCH₂C H ₂C H ₂C H ₂C H ₂).

1.2.9. Preparation of 4- (3-hydroxypropyaminol) -2-nitro-N, N-dimethyaniline Stage a) 4-amino-2-nitro-N, N-dimethylaniline

The preparation was carried out according to the instructions in Example 1.2.1.

Step b) 4- (3-Chloropropoxy-carbonylamino) -2-nitro-N, N-dimethylaniline

The preparation in stage b) was carried out analogously to Example 1.2.2. Stage b) by reacting 4-amino-2-nitro-N, N-dimethylaniline with 3-chloropropyl chloroformate.
Yield: 36.1 g (74.8% of theory)
Melting point: (oil)
IR: 3328 cm ^-1 (ν CH _Ar ), 2963, 2806 cm ^-1 (ν CH), 1708 cm ^-1 (ν C = O), 1582 cm ^-1 (C = C), 1537 cm ^-1 (ν _as NO₂), 1350 cm ^-1 (νs NO₂), 1225 cm ^-1 (ν OC).
1 H-NMR: 9.8 ppm (1H, s, NH); 7.99 ppm (H3, s); 7.55 (H⁵, dd, ³J _{H, H} = 9.03 Hz, ⁴J _{H, H} = 2.21 Hz); 7.18 ppm (H, d, 3 _{H, H} = 8.80 Hz); 4.22 ppm (2H, t, 3 J _{H, H} = 6.12 Hz, C (O) OC H ₂); 3.74 ppm (2H, t, 3 J _{H, H} = 4.98 Hz, CH₂Cl); 2.75 ppm (6H, s, N (CH₃) ₂); 2.10 ppm (2H, m, OCH₂C H ₂CH₂Cl).

Step c) 4- (3-Hydroxypropylaminol) -2-nitro-N, N-dimethyaniline

The implementation of stage c) was carried out analogously to Example 1.2.2. Step c) by reaction of 4- (3-chloropropoxycarbonylamino) -2-nitro-N, N-dimethylaniline with sodium hydroxide solution.
Yield: 20.9 g (73.3% of theory).

1.2.10. Preparation of N- [4- (3-hydroxypropylamino) -2-nitrophenyl] morpholine Stage a) N- (4-amino-2-nitrophenyl) morpholine

The product was prepared according to Example 1.2.1. made, however, was replaced by Dime thylamine now used morpholine.

Step b) N- [4- (3-Chloroprnopoxycarbonylamino) -2-nitrophenyl] morpholine

The execution of stage b) was carried out analogously to Example 1.2.2. Step b) by reacting N- (4-amino-2-nitrophenyl) morpholine with 3-chloropropyl chloroformate.
Yield: 32.7 g (95.1% of theory)
Melting point 122-124 ° C
IR: 3245 cm ^-1 (ν CH _Ar ), 2964 cm ^-1 (ν CH), 1737 cm ^-1 (ν C = O), 1596 cm ^-1 (C = C), 1537 cm ^-1 (ν _as NO₂ ), 1373 cm ^-1 (ν _s NO 2), 1221 cm ^-1 (ν OC).
1 H-NMR: 9.95 ppm (1H, s, NH); 7.99 ppm (H3, s); 7.62 (H⁵, dd, ³J _{H, H} = 8.81 Hz, ⁴J _{H, H} = 1.81 Hz); 7.38 ppm (H, d, 3 _{H, H} = 8.93 Hz); 4.23 ppm (2H, t, 3 _{H, H} = 6.18 Hz, C (O) OC H ₂); 3.75 ppm (2H, t, 3 J _{H, H} = 6.43 Hz, CH₂Cl); 3.69 ppm (4H, t, 3 J _{H, H} = 4.08 Hz, CH₂OCH₂); 2.93 ppm (4H, t, 3 _{H, H} = 4.06 Hz, CH₂NCH₂); 2.10 ppm (2H, q, 3 J _{H, H} = 6.27 Hz, CH₂C H ₂CH₂).

Step c) N- [4- (3-hydroxypropylamino) -2-nitrophenyl] morpholine

In step c) was analogous to Example 1.2.2. Step c) N- [4- (3-chloropropoxycarbonylamino) -2-nitrophenyl] morpholine is reacted with sodium hydroxide solution.
Yield: 20.4 g (90.5% of theory)
Melting point: 93-95 ° C
IR: 3433, 3347 cm ^-1 (ν CHM), 2964, 2867 cm ^-1 (ν CH), 1622 cm ^-1 (ν C = C), 1543 cm ^-1 (ν _as NO₂), 1371 cm ^-1 (ν _s NO₂).
¹H-NMR: 7.24 ppm (H⁶, d, ³J _{H, H} = 8.55 Hz); 6.84 ppm (H3, d, ⁴JH _{, H} = 2.52 Hz); 6.81 ppm (H⁵, dd, ³J _{H, H} = 8.59 Hz, ⁴J _{H, H} = 2.72 Hz); 6.03 ppm (1H, t, 3 J _{H, H} = 5.46 Hz, OH); 3.63 ppm (4H, t, 3 J _{H, H} = 4.49 Hz, CH₂OCH₂); 3.49 ppm (2H, t, 3 J _{H, H} = 6.21 Hz, C H ₂OH); 3.06 ppm (2H, q, 3 J _{H, H} = 6.75 Hz, 3 J _{H, H} = 12.53 Hz, NC H ₂CH₂CH₂OH); 2.81 ppm (4H, t, 3 J _{H, H} = 4.49 Hz, CH₂NCH₂); 1.67 ppm (2H, q, ³J _{H, H} = 6.56 Hz, NCH₂C H ₂CH₂OH).

1.2.11. Preparation of N- [4- (3-hydroxypropylamino) -2-nitrophenyl] piperidine Stage a) N- (4-amino-2-nitrophenyl) piperidine

The reaction is carried out using piperidine and 4-fluoro-3-nitraniline in Analogy to Example 1.2.1.

Step b) N- [4- (3-Chloropropoxycarbonylamino) -2-nitropheny] piperidine

Stage b) is analogous to Example 1.2.2. Stage b), but N- (4-amino-2-nitrophenyl) piperidine and 3-chloropropyl chloroformate were reacted.
Yield: 20.6 g (60.4% of theory)
Melting point: (oil)
IR: 3331 cm ^-1 (ν CH _Ar ), 2938, 2854 cm ^-1 (ν CH), 1708 cm ^-1 (ν C = O), 1587 cm ^-1 (C = C), 1532 cm ^-1 (ν _as NO₂), 1305 cm ^-1 (ν _s NO₂), 1224 cm ^-1 (ν OC).
1 H-NMR: 9.95 ppm (1H, s, NH); 7.95 ppm (H⁶, d, ³J _{H, H} = 1.71 Hz); 7.57 ppm (H⁵, dd, ³J _{H, H} = 8.87 Hz, ⁴J _{H, H} = 2.05 Hz); 7.28 ppm (H 3, d, 3 _{H, H} = 8.89 Hz); 4.21 ppm (2H, t, 3 _{H, H} = 6.19 Hz, C (O) OC H ₂); 3.73 ppm (2H, t, 3 J _{H, H} = 6.44 Hz, CH₂Cl); 2.85 ppm (4H, t, 3 J _{H, H} = 4.83 Hz, CH₂NCH₂); 1.57 ppm (4H, m, C H ₂CH₂C H ₂); 1.49 ppm (2H, m, CH₂C H ₂CH₂).

Step c) N- [4- (3-Hydroxypropylamino) -2-nitrophenyl] piperidine

The execution of stage c) was carried out analogously to Example 1.2.2. Step c) by reacting N- [4- (3-chloropropoxycarbonylamino) -2-nitrophenyl] piperidine with potassium hydroxide solution.
Yield: 13.9 g (83.1% of theory)

1.2.12. Preparation of Preparation of N- [4- (3-hydroxypropylamino) -2-nitrophe nyl] pyrrolidine Stage a) N- (4-amino-2-nitrophenyl) pyrrolidine

The procedure was carried out in analogy to Example 1.2.1. under the use of Pyrrolidine instead of dimethylamine.

Step b) N- [4- (3-Chloropropoxycarbonylamino) -2-nitrophenyl] pyrolidine

The implementation of stage b) was carried out analogously to Example 1.2.2. Step b) by reaction of N- (4-amino-2-nitrophenyl) pyrrolidine with 3-chloropropyl chloroformate.
Yield: 23.7 g (72.2% of theory)
Melting point: (oil)
IR: 3331 cm ^-1 (ν CH _Ar ), 2967, 2873 cm ^-1 (ν CH), 1703 cm ^-1 (ν C = O), 1578 cm ^-1 (C = C), 1533 cm ^-1 (ν _as NO₂), 1365 cm ^-1 (ν _s NO₂), 1226 cm ^-1 (ν OC).
1 H-NMR: 9.7 ppm (1H, s, NH); 7.96 ppm (H⁶, s); 7.49 ppm (H⁵, dd, ³J _{H, H} = 9.07 Hz, ⁴J _{H, H} = 2.04 Hz); 6.98 ppm (H 3, d, 3 _{H, H} = 9.24 Hz); 4.20 ppm (2H, t, 3 J _{H, H} = 6.22 Hz, C (O) OC H ₂); 3.73 ppm (2H, t, 3 _{H, H} = 6.46 Hz, CH₂Cl); 3.09 ppm (4H, t, 3 J _{H, H} = 6.05 Hz, CH₂NCH₂); 2.08 ppm (2H, q, ³J _{H, H} = 6.35 Hz, CH₂C H ₂CH₂Cl); 1.88 ppm (4H, m, ³J _{H, H} = 6.27 Hz, CH₂CH₂).

Step c) N- [4- (3-Hydroxypropylamino) -2-nitrophenyl] pyrrolidine

Stage c) was analogous to Example 1.2.2. Step c), but N- [4- (3-chloropropoxycarbonylamino) -2-nitrophenyl] pyrrolidine and potassium hydroxide were reacted.
Yield: 13.3 g (69.9% of theory)

1.2.13. Preparation of N- [4- (3-hydroxyethylamino) -2-nitrophenyl] azepane Stage a) N- (4-amino-2-nitrophenyl) azepane

The compound was as in Example 1.2.8. specified manufactured.

Step b) N- [4- (3-Chloropropoxycarbonylamino) -2-nitrophenyl] azeoane

Stage b) was analogous to Example 1.2.2. Stage b), but N- (4-amino-2-nitrophenyl) azepane and 3-chloropropyl chloroformate were reacted.
Yield: 32.7 g (95.1% of theory)
Melting point: 61-63 ° C
IR: 3395, 3098 cm ^-1 (ν CH _Ar ), 2928, 2856 cm ^-1 (ν CH), 1726 cm ^-1 (ν C = O), 1574 cm ^-1 (ν C = C), 1533 (ν _as NO₂), 1354 cm ^-1 (ν _s NO₂), 1226 cm ^-1 (ν O-C).
1 H-NMR: 9.75 ppm (1H, s, NH); 7.90 ppm (H3, s); 7.48 ppm (H⁵, dd, ³J _{H, H} = 9.08 Hz, ⁴J _{H, H} = 1.89 Hz); 7.15 ppm (H⁶, d, ⁴J _{H, H} = 9.17 Hz); 4.20 ppm, 4.23 ppm (2H, t, 3 _{H, H} = 6.17 Hz, C (O) OC H ₂); 3.72 ppm (2H, t, 3 _{H, H} = 6.44 Hz, CH₂Cl); 3.13 ppm (4H, t, 3 J _{H, H} = 5.44 Hz, CH₂NCH₂); 2.08 ppm (2H, m, OCH₂C H ₂CH₂Cl); 1.67 ppm (4H, s, NCH₂C H ₂); 1.49 ppm (4H, s, NCH₂CH₂C H ₂).

Step c) N- [4- (3-Hydroxyetylamino) -2-nitrophenyl] azepane

It was prepared by reacting N- [4- (3-chloropropoxycarbonylamino) -2-nitrophenyl] azepane with sodium hydroxide solution.
Yield: 12.8 g (34.3% of theory)

1.2.14. Preparation of N- {4- [di- (2-hydroxyethyl) amino] -2-nitrophenyl} pyrrolidine

In 65 ml of 1,2-dimethoxyethane, 24.4 g (0.1 mol) of 4-fluoro-3-nitro-N, N-di- (2-hydroxyethyl) -aniline, 7.8 g (0.11 Mol) pyrrolidine, 5.3 g (0.05 mol) of potassium carbonate and 0.25 g of methyl tri (C₆-C₈) alkylammonium chloride (70% in isopropanol) and heated under reflux until the reaction was complete. The undissolved salts were filtered off in the heat and the mother liquor was cooled. The precipitated product was filtered off with suction and dried.
Yield: 23.8 g (80.6% of theory)
IR: 3401 cm ^-1 (ν CH _Ar ), 2965, 2870 cm ^-1 (ν CH), 1630 cm ^-1 (ν C = C), 1547 (ν _as NO₂), 1358 cm ^-1 (ν _s NO₂) ,
1 H-NMR: 7.02 ppm (H 3 H⁵H⁶, m); 4.73 (2H, t, 3 J _{H, OH} = 5.38 Hz, CH₂O H ); 3.53 ppm (4H, q, 3 J _{H, H} = 6.34 Hz, CH₂OH); 3.36 ppm (4H, t, ³J _{H, H} = 5.74 Hz, NC H ₂CH₂OH); 3.04 ppm (4H, t, 3 J _{H, H} = 6.39 Hz, NCH₂); 1.88 ppm (4H, t, ³J _{H, H} = 6.42 Hz, NCH₂ CH₂CH₂).

2. colorations 2.1. Colorants on a cream basis

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   Cetylstearylalcohol 12.0 g myristyl 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)

(I-1) N- (4-amino-2-nitrophenyl) morpholine
(I-2) N- (4-amino-2-nitrophenyl) piperidine
(I-3) N- (4-amino-2-nitrophenyl) pyrrolidine
(I-4) N- (4-amino-2-nitrophenyl) azepane

2.3. Oxidation dye precursors

- Developer component:
(E-1) 2,5-diaminotoluene sulfate
Coupler component:
(K-1) 2-Amino-4-hydroxyethylamino-anisole sulfate
(K-2) 2-methylresorcinol

2.4. method

50 g of the colorant (in the case of the recipe with the oxidation dye precursors shortly before use with 50 g H₂O₂ solution (6% in water) mixed) were applied by a brush to 100% gray hair (4 g colorant per g hair). After a residence time of 30 minutes at room temperature, the colorant became rinsed and dried the hair.  

2.5. Results

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

2.6 Application examples Coloring cream 1 Compound (I-1) 3.0 g Sodium lauryl sulfate (70%) 2.0 g oleic acid 2.0 g Sodium sulfite, anhydrous 0.6 g stearyl 10.0 g myristyl 6.0 g propylene glycol 1.0 g Ammonia, 25% 8.0 g Water, ad 100 g

Coloring cream 2 Compound (I-2) 1.5 g Sodium lauryl sulfate (70%) 3.0 g   oleic acid 2.0 g Sodium sulfite, anhydrous 0.6 g Cetylstearylalcohol 10.0 g myristyl 6.0 g ethylene glycol 1.0 g Ammonia, 25% 11.0 g Water, ad 100 g

Coloring cream 3 Compound (I-4) 3.0 g Sodium lauryl sulfate (70%) 1.5 g oleic acid 3.5 g sodium 0.3 g Cetylstearylalcohol 15.0 g myristyl 6.0 g propylene glycol 1.5 g Ammonia, 25% 14.0 g Water, ad 100 g

Coloring cream 4 Compound (I-1) 2.1 g Rodol 9 R 0.2 g Sodium lauryl sulfate (70%) 3.0 g oleic acid 1.0 g Sodium sulfite, anhydrous 0.7 g Cetylstearylalcohol 13.0 g myristyl 6.0 g ethylene glycol 1.0 g Ammonia, 25% 10.0 g Water, ad 100 g

Dye cream 5 Compound (I-2) 2.3 g HC Yellow 2 @ or HC Yellow 4 @ or HC Yellow 12 1.0 g Sodium lauryl sulfate (70%) 4.0 g oleic acid 1.0 g ascorbic acid 0.5 g Cetylstearylalcohol 10.0 g myristyl 6.0 g propylene glycol 1.5 g Ammonia, 25% 10.0 g Water, ad 100 g

Coloring cream 6 Compound (I-3) 2.0 g HC Red BN 0.5 g HC Blue 2 0.1 g Sodium lauryl sulfate (70%) 1.5 g oleic acid 2.0 g Sodium sulfite, anhydrous 0.6 g Cetylstearylalcohol 12.5 g myristyl 6.0 g propylene glycol 1.0 g Ammonia, 25% 14.0 g Water, ad 100 g

Coloring cream 7 Compound (I-3) 2.5 g   6-nitro-1,2,1,4-tetranydrochinoxalin 0.3 g Sodium lauryl sulfate (70%) 2.0 g oleic acid 3.0 g Sodium sulfite, anhydrous 1.0 g Cetylstearylalcohol 15.0 g myristyl 6.0 g propylene glycol 1.0 g Ammonia, 25% 7.0 g Water, ad 100 g

Dye cream 8 Compound (I-3) 0.5 g Coupler (K-1) 1.5 g Developer (E-1) 1.05 g Sodium lauryl sulfate (70%) 2.5 g oleic acid 1.5 g Sodium sulfite, anhydrous 0.8 g Cetylstearylalcohol 12.0 g myristyl 6.0 g propylene glycol 1.0 g Ammonia, 25% 10.0 g Water, ad 100 g

Claims (10)

1. agent for dyeing keratin fibers, characterized in that as a substantive dye, a 2-nitroaniline derivative of the general formula (I), in which R₁, R₂, R₃ and R₄ are independently
a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamoylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulfalkyl, piperidinoalkyl, morpholinoalkyl or phenyl radical, optionally in the para position with an amino group substituted, these alkyl or alkoxy groups having one to four carbon atoms, with the proviso that not all four substituents R₁, R₂, R₃ and R₄ are simultaneously hydrogen,
and the groups -NR₁R₂ and / or -NR₃R₄ can also be an aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, morpholine, thiomorpholine or a piperazine ring, which also has another on the nitrogen atom Substituents R₈, wherein R₈ is a hydrogen atom, a (C₁-C₄) alkyl, a hydroxy (C₂-C₃) alkyl, a (C₁-C₄) alkoxy (C₂-C₃) alkyl, is an amino (C₂-C₃) alkyl or a 2,3-dihydroxypropyl group,
and R₅, R₆ and R₇ independently represent a hydrogen atom, a (C₁-C₄) alkyl, a (C₁-C₄) alkoxy, a carboxy, sulfo or a (C₂-C₄) hydroxyalkyl, or a physiologically acceptable salt of these compounds is contained with an inorganic or organic acid. 2. Agent for dyeing keratin fibers, characterized in that a direct-acting dye is a 2-nitroaniline derivative of the general formula (I) in which R₁, R₂, R₃ and R₄ independently represent a hydrogen atom, an alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, Ace tylaminoalkyl-, Ureidoalkyl-, Carbalkoxyaminoalkyl-, sulfalkyl, Piperidinoalkyl-, Morpholinoalkyl- or a phenyl radical, optionally substituted in the para position with an amino group, said alkyl or alkoxy groups having one to four carbon atoms, with the proviso that not all four substituents R₁, R₂, R₃ and R₄ are simultaneously hydrogen, and the groups -NR₁R₂ and or -NR₃R₄ can also be an aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, morpholine, thiomorpholine or a piperazine ring, which can also carry a further substituent R₈ on the nitrogen atom, wherein R₈ is a hydrogen atom, a (C₁-C₄) alkyl, a hydroxy (C₂-C₃) alkyl, a (C₁-C₄) alkoxy (C₂-C₃) alkyl, an amino (C₂-C₄) alkyl, C₃) alkyl or a 2,3-dihydr oxypropyl is, with the proviso that in the event that only one of the two groups -NR₁R₂ or -NR₃R₄ is such a ring system, - The other substituents R₃ and R₄ or R₁ and R₂ independently vonein Other may also stand for hydrogen, a (C₁-C₄) alkyl or a (C₂-C₃) - Hydroxyalkyl group and at least one of the substituents R₅, R₆ or R₇ does not stand for hydrogen, and R₅, R₆ and R₇ independently represent a hydrogen atom, a (C₁-C₄) - Alkyl, a (C₁-C₄) alkoxy, a carboxy, sulfo or a (C₂-C₄) -Hy hydroxyalkyl, or a physiologically acceptable salt of these  Contains compounds with an inorganic or organic acid. 3. Composition according to claim 1 or 2, characterized in that the group -NR₁R₂ for an aziridine, azetidine, pyrrolidine, piperidine, azepane, azocine, morpholine, Thiomorpholine or a piperazine ring, which on the nitrogen also a wide Ren substituents R₈, where R₈ is a hydrogen atom, a (C₁-C₄) -Al kyl, a hydroxy (C₂-C₃) alkyl, a (C₁-C₄) alkoxy (C₂-C₃) alkyl, an amino (C₂-C₃) alkyl or a 2,3-dihydroxypropyl group is. 4. Composition according to one of claims 1 to 3, characterized in that the verbin in accordance with formula (I) in amounts of from 0.001 to 10% by weight, in particular of 0.1 to 5 wt .-%, based on the total agent is included. 5. Composition according to one of claims 1 to 4, characterized in that it has a contains further substantive dye. 6. Composition according to one of claims 1 to 5, characterized in that it continues contains a developer-type oxidation dye precursor. 7. Composition according to one of claims 1 to 6, characterized in that it continues a coupler-type oxidation dye precursor. 8. Use of 2-nitroanilines of the general formula (I) according to claim 1 or 2 for coloring keratinic fibers.