DE3325790A1 - Process for the preparation of 4-amino-3-nitrophenol derivatives, novel 4-amino-3-nitrophenol derivatives and compositions for dyeing hair - Google Patents

Abstract

Process for the preparation of 4-amino-3-nitrophenol derivatives of the general formula I <IMAGE> in which R represents a straight-chain or branched, unsubstituted or substituted alkyl radical, by reaction of the corresponding 4-chloro-3-nitrophenol ether with a primary alkylamine and subsequent acidic ether cleavage. The invention further relates to novel 4-amino-3-nitrophenol derivatives of the general formula V <IMAGE> in which R<1> denotes an alkyl radical of the formula CnH(2n+1) where n = 2-6, or an alkyl radical of the formula -(CH2)p-U-(CH2)q-H interrupted by a heteroatom where U = O or S, p = 2-3 and q = 2-3, or an alkyl radical of the formula CrH(2r+1-s)(OH)s substituted by one or more OH groups where r = 3-6 and s = 1-3, and compositions for dyeing hair containing the red-dyeing nitro dyestuffs of the formula V.

Description

Process for the preparation of 4-amino-3-nitrophenolderi-

vaten, new 4-amino-3-nitrophenol derivatives and means for coloring Hair Nitrogen dyes have found widespread use in hair dyes today. They have the advantage of protecting the hair shaft due to their relatively low molecular weight to penetrate and enable intensive staining.

Part of the well-known yellow, red, purple and blue nitro dyes can also be combined in such a way that with such recipe combinations on different Hair qualities that are usually increasingly damaged from roots to ends reproducible and even, natural colors can be produced. Good colorations are achieved up to a gray proportion of the hair of about 30%, without combining the nitro dyes with the so-called oxidation dyes Need to become.

With a higher proportion of gray, natural tones must be created Oxidation hair dyes are used with good coverage and good color levelness, to their most important representatives the so-called developers and the so-called Include coupler substances. The main developer substances are p-substituted ones Benzene derivatives such as 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminobenzyl alcohol, 2,5-diaminophenol ether, 2,6-dimethyl-1,4-diaminobenzene 1- (2'-hydroxyethyl) -2,5-diaminobenzene and p-aminophenol into consideration.

Resorcinol, 2-methylresorcinol, 4-chlororesorcinol, m-aminophenol, 5-amino-2-methylphenol and derivatives of m-phenylenediamine, such as B. 2,4-diaminoanisole or 2-amino-4- (2'-hydroxyethylamino) anisole, proven. In addition, substituted pyridines can also be used advantageously as coupler substances furthermore 4-hydroxy-1,2-methylenedioxybenzene, 4-amino-1,2-methylenedioxybenzene, 4- (2'-hydroxyethylamino) -1, 2-methylenedioxybenzene, 1-naphthol, 4-hydroxyindole, 2,4-dihydroxyphenol ether, 4,6-dichlororesorcinol, 4-bromoresorcinol and others can be used.

In the field of yellow and orange coloring nitro dyes is so far a large number of different compounds described in the literature and partially has also been used in hair dyes. However, the opposite is in the field the red coloring nitro dyes the case where there is a marked shortage of suitable ones Connections exist.

The required red dyes must be as intense and relevant as possible their coloration deliver uniform red tones, which are not as bluish or tinged as possible should be orange. For the use of the red coloring nitro dyes in In addition, a high luminosity of the colors is of great interest in fashion shades. The requirements outlined are approximately met by 4- (2'-hydroxyethylamino) -3-nitrophenol fulfilled, a compound that is described in German patent application 2,717,766 is. The synthetic method described in the cited patent application for this compound however, is specifically geared towards 2'-hydroxyalkylation on the amino nitrogen and does not allow the production of diverse molecular variants in which the hydroxyalkyl radical is replaced by other groups.

In contrast, a new synthesis process has now been found with the general formula I 4-amino-3-nitrophenol derivatives where R represents a straight-chain or branched, unsubstituted or substituted alkyl radical, can be prepared.

Examples of substituted alkyl radicals are an aminoalkyl group, a dimethylaminoalkyl group, a methyl mercaptoethyl group, a methylsulfonylethyl radical, an alkoxyethyl radical, a dihydroxyalkyl radical and a hydroxyalkyl group (e.g. 3-hydroxypropyl-) to call.

In the process according to the invention, the starting compounds are used 4-chloro-3-nitroanisole (III a) or 4-chloro-3-nitrophenol (IV), which in one Phenol ether (III b), preferably converted into the benzyl or t-butyl phenol ether (see reaction scheme below). The above-mentioned starting compounds are known. Their production is z. B. in Beilstein's manual of the organic Chemie Volume 6, E III (1965), page 838 and Volume 6 (1923), page 239.

Reaction scheme: In the chlorophenol ethers (III a) or (III b), the chlorine is nucleophilically exchanged in a further reaction step for a primary alkylamine H2NR, where R has the meaning given above. The exchange is surprisingly possible with a large number of primary aliphatic amines, it also being possible for the aliphatic radical to be substituted by an aryl radical. In the present context, the exchange reaction with the primary aliphatic amines is of particular interest. Examples of these amines are n-butylamine, 1,3-diaminopropane, 1,2-diaminoethane, 2-dimethylaminoethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, 2-methylmercaptoethylamine, 2-amino-1-butanol, 4-amino-1-butanol, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-amino-1-propanol and 1-amino-2,3-propanediol should be mentioned; however, the possible substitutions are not limited to these amines alone. The reaction is preferably carried out at a temperature of from 120 to 1500.degree.

The last reaction step is the 4- (N-alkylamino) -3-nitrophenols of the formula I by acidic ether cleavage from the 4- (N-alkylamino) -3-nitrophenol ethers (II a) or (II b) set free. In the case of the methyl ether (II a), this can by cooking with mineral acids or with aluminum chloride in benzene while the benzyl and t-butyl ethers (II b) easily by briefly heating with 60% strength Sulfuric acid are cleavable.

The described new synthesis method is with regard to its generality and flexibility of the method described in German patent application 2 717 766, which is limited only to a hydroxyethylation, clearly superior and leads to a whole class of new, red-coloring nitro dyes, their properties can be varied as required by a suitable choice of the substituent R.

The present patent application therefore continues to provide new 4-amino-3-nitrophenol derivatives of the general formula V where R1 is an alkyl radical of the formula CnH CnH (2n + 1) with n = 2-6 or an alkyl radical of the formula - (CH2) p - U ~ (CH2) q ~ H with U = 0 or S, p = 2-3 and q = 2-3 or an alkyl radical of the formula CrH (2r + 1-s) (OH) 5 with one or more OH groups substituted with r = 3-6 and s = 1-3.

Examples of new compounds of the general formula V are 4-butylamino-3-nitro-phenol 4- (2'-methoxyethylamino) -3-nitro-phenol 4- (2'-hydroxypropylamino) -3-nitro-phenol 4- (2 ', 3'-dihydroxypropylamino) -3-nitro-phenol 4- (3'-hydroxypropylamino) -3-nitro-phenol 4- (2'-Methylmercaptoethylamino) -3-nitro-phenol The new compounds according to the invention of the general formula V represent the coloring of keratin, especially human Hair, are excellent nitro dyes.

The present application therefore also relates to agents for coloring hair with a dye content and usual cosmetic Additives, characterized in that they contain at least one 4-amino-3-nitrophenol derivative of the general formula V included.

The agents according to the invention for coloring hair relate to both those that are used without the addition of an oxidizing agent, as well as those, which require the addition of an oxidizing agent.

In the case of the former hair dyes without the addition of oxidizing agents these are those that, in addition to the dyes of the given formula, have other may contain dyes that are absorbed directly onto the hair. Of these for the The following dyes known to hair coloring may be mentioned, for example: Aromatic Nitro dyes, such as 2-amino-4-nitrophenol, picric acid, 1- (2-hydroxyethylamino) -2-amino-4-nitrobenzene, 2-nitro-4- (2'-hydroxyethylamino) -aniline, 1-methylamino-2-nitro-4-bis- (2'-hydroxyethyl) -aminobenzene and 1,2-diamino-4-nitrobenzene; Triphenylmethane dyes such as Basic Violet 1 (C.I. 42 535); Azo dyes such as Acid Brown 4 (C.I. 14 805); Anthraquinone dyes, such as, for example, Disperse Violet 4 (C.I. 61 105), 1,4,5,8-tetraaminoanthraquinone and 1,4-diaminoanthraquinone, the dyes of these classes depending on their nature Substituents can have acidic, nonionic or basic character. Further suitable dyes which are absorbed directly onto the hair are, for example, in Book by J.C. Johnson, "Hair Dyes" Noyes Data Corp. Park-Ridge (USA) (1973).

The preparation form of the hair dyes described here on the The basis of dyes that are absorbed directly onto the hair can, for example, be a Solution, especially an aqueous or aqueous-alcoholic solution. Before- drew Preparation forms are also a cream, a gel or an emulsion, whereby they can also be sprayed in a mixture with a propellant gas or by means of a pump can.

The dyes of the formula V given are intended to be used in these colorants in a concentration of about 0.01 to 2.0% by weight, preferably from 0.01 to 1.0 % By weight. The total content of colorants is within the limits of about 0.01 to 3.0% by weight.

The pH of these colorants is in the range from 7 to 10.5, in particular at pH 7.5 to 9.5, the adjustment of the desired pH being mainly takes place with ammonia, but also with organic amines such as monoethanolamine or triethanolamine can be made.

They are used in the usual way by applying the agent on the hair that has been in contact with for a time, between 5 and 30 minutes remain. Then with water, optionally also with the aqueous solution a weak organic acid, rinsed and dried. As weak organic Acid, for example, acetic acid, citric acid, tartaric acid and similar uses Find.

The hair dyes described above without the addition of oxidizing agents can of course also contain cosmetic polymers, whereby at the same time the coloring strengthens the hair. Such means are used in the generally referred to as tint setter or color setter.

Of the polymers known for this purpose in cosmetics be for example polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic compounds such as acrylic acid or methacrylic acid polymers, basic polymers of esters from these two acids and amino alcohols or their salts or quaternization products, polyacrylonitrile, polyvinyl lactams and copolymers from such compounds as polyvinylpyrrolidone vinyl acetate and the like mentioned.

Also natural polymers like chitosan (deacetylated chitin) or Chitosan derivatives can be used for the stated purpose.

The polymers are in these agents in the usual amount of contain about 1 to 4 wt.%. The pH values of the agents are in the range of about 6.0 to 9.0.

These hair dyes are used with additional setting in a known and customary manner by moistening the hair with the setting agent, setting <Inserting) the hair to the hairstyle and subsequent drying.

Of course, the hair dyes described above can be used without the addition of oxidizing agents, other common cosmetic additives, if applicable such as care substances, wetting agents, thickeners, plasticizers and perfume oils as well as other common ones listed below for oxidation hair dyes Supplements included.

The subject matter of the present invention also includes, as at the beginning mentioned those hair dyes that require the addition of an oxidizing agent is required.

In addition to the dyes, they contain the specified formula V also known oxidation dyes that undergo oxidative development need.

These oxidation dyes are mainly aromatic p-diamines and p-aminophenols such as p-toluylenediamine, p-phenylenediamine, p-aminophenol and similar compounds, which are used for the purpose of shading the colorations with so-called modifiers, such as B. m-phenylenediamine, resorcinol, m-aminophenol and others can be combined.

Oxidation dyes of this type which are known and customary for coloring hair are among others in the book by E. Sagarin, "Cosmetics", Science and Technology (1957), Interscience Publishers Inc., New York, pages 503 ff. And in the book by H. Janistyn, Handbook of Cosmetics and Fragrances "(1973) pages 338 ff., described.

With mixtures of these oxidation dyes and the new dyes According to the given formula V, in addition to pure fashionable tones, fashionable ones can also be used Preserved blonde and brown tones.

The dyes according to the formula V are included in these colorants Oxidizing agent addition in a concentration of about 0.01 to 4.0% by weight, preferably 0.02 to 2.0% by weight. The total content of colorants in these colorants is about 0.1 to 5.0% by weight.

Oxidation hair dyes are generally made alkaline, preferably to pH values of about 8.0 to 11.5, the setting in particular done with ammonia. But it can also use other organic amines such. B. monoethanolamine or triethanolamine, use. As an oxidizing agent to develop the Hair coloring comes mainly from hydrogen peroxide and its addition compounds into consideration. The preparation form of these hair dyes can be the same as that of Hair dye without the addition of oxidizing agents. Preferably is it that of a cream or gel.

Usual additives in creams, emulsions or gels are for example Solvents such as water, lower aliphatic alcohols, for example ethanol, Propanol, isopropanol, glycerine or glycols such as ethylene glycol and propylene glycol, or also glycol ethers, furthermore wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surface-active substances such as fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl sulfonates, alkyl benzene sulfates, Alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated Nonylphenols, fatty acid alkanolamides, ethoxylated fatty acid esters, and also thickeners such as higher fatty alcohols, bentonite, starch, polyacrylic acid, cellulose derivatives, such as Carboxymethyl cellulose, alginates, petrolatum, paraffin oil and fatty acids as well as well Care substances such as lanolin derivatives, cholesterol, pantothenic acid and betaine, as well Perfume oils and complexing agents. The mentioned components are in the for such Purposes usual amounts used, for example the wetting agents and emulsifiers in Concentrations of about 0.5 to 30 wt.%, While the thickeners in an amount The preparations can contain from about 0.1 to 25% by weight.

The preparations mentioned are used in a known manner, by mixing the hair dye with the oxidizing agent prior to treatment and applying the mixture to the hair.

After an exposure time sufficient for the hair coloring, which usually about 10 to 45 minutes, is followed by with water, if necessary with the aqueous solution of a weak organic acid, such as for example Citric acid or tartaric acid, rinsed and dried.

With regard to the possibilities of dyeing, those according to the invention offer Hair dye depending on the type and composition of the color components a wide range Range of different shades of color, ranging from natural shades to highly fashionable, luminous nuances.

Depending on their composition, the colorants are either in Used in conjunction with hydrogen peroxide or without oxidizing agents.

The following examples are intended to explain the subject of the application, without limiting it to it.

PREPARATION EXAMPLES Example 1 Preparation of 4- (2'-methoxyethylamino) -3-nitro-phenol Reaction scheme: Stage 1 200 ml of water, 4.8 g (0.12 mol) of sodium hydroxide, 200 ml of methylene chloride, 14.0 g (0.08 mol) of 4-chloro-3-nitrophenol, 13.7 g of benzyl bromide and 3.2 g Benzyltributylammonium bromide are combined in the order given.

The mixture is stirred vigorously for 6 hours. Then the methylene chloride phase separated and evaporated.

The residue is mixed with 200 ml of water and three times with 100 each ml of diethyl ether extracted. The ether phase is washed with water and over magnesium sulfate dried.

The residue that remains when the ether phase is concentrated is recrystallized from 60 ml of methanol. 15.0 g (71% of theory) of 4-chloro-3-nitro-phenol benzyl ether are obtained with a melting point of 50.5 to 51.50 C.

Stage 2 0.5 g of 4-chloro-3-nitrophenol benzyl ether are mixed with 10 ml of 0 2-Methoxyethylamine heated to 150 ° C. in an autoclave.

After 24 hours the mixture was cooled and the 2-methoxyethylamine was distilled off. The residue is chromatographed on silica gel. With methylene chloride as the mobile phase 0.26 g (44% of theory) of the red 4- (2'-methoxyethylamino) -3-nitrophenolbenzyl ether are obtained from melting point 78 to 79 ° C.

CHN analysis% C% H% N C16H18N204 calculated: 63.56 6.00 9.27 found: 63.00 6.04 9.25 Stage 3 0.1 g of 4- <2'-methoxyethylamino) -3-nitrophenol benzyl ether from stage 2 are heated to 800 ° C. with 5 g of 60% strength sulfuric acid. After 10 minutes the mixture is made with 20 ml Water mixed with sodium hydrogen carbonate neutralized and extracted with ether. 60 mg (85%) are obtained from the ether phase % of theory) of a slowly crystallizing oil.

CHN analysis% C% H% N C9H12N204 calculated: 50.94 5.70 13.20 found: 51.02 5.75 13.42 Example 2 Preparation of 4- (2'-hydroxypropylamino) -3-nitro-phenol Reaction scheme: Stage 1 0.5 g of 4-chloro-3-nitrophenol benzyl ether are heated to 1200 ° C. for 2 hours with 5 ml of 1-amino-2-propanol. 10 ml of water are added and the reaction product is extracted with ether. 0.51 g (89% of theory) of an oily reaction product consisting of 4- (2'-hydroxypropylamino) -3-nitro-phenol benzyl ether is obtained.

Stage 2 The reaction product from stage 1 is treated with 60% sulfuric acid heated to 800 C. After 10 minutes, 20 ml Water added. After extraction with ether, 0.3 g (84% of theory) of 4- (2'-hydroxypropylamino) -3-nitrophenol are obtained obtain.

CHN Analysis% C% H% N C9H12N204 calculated: 50.94 5.70 1-, 20 found: 50.71 5.68 13.19 Example 3 Preparation of 4- (2 ', 3'-dihydroxypropylamino) = 3 -nitrophenol reaction scheme: Stage 1 0.5 g of 4-chloro-3-nitrophenol benzyl ether are heated to 1300 ° C. for 4 hours with 5 ml of 3-amino-1,2-propanediol.

After working up as in Example 2 / Stage 1, 0.46 g (76 (76% of theory) oily reaction product obtained.

Stage 2 The reaction product from stage 1 is treated with 60% sulfuric acid heated to 800 C. After 10 minutes, 20 ml of water are added. By extraction with diethyl ether and subsequent processing as in Example 1 themselves 0.26 g (79% of theory) of the desired 4- (2 ', 3'-dihydroxypropylamino) -3-nitro-phenol isolate.

CHN Analysis% C% H% N C9H12N205 Calculated: 47.37 5.30 12.28 Found: 47.50 5.40 12.42 Example 4 Preparation of 4- (3'-Xydroxypropylamino) -3-nitro-phenol Reaction scheme: Stage 1 19.0 g (0.1 mol) of 4-chloro-3-nitroanisole and 100 ml (1.3 mol) of 3-amino-1-propanol are heated to 1200 ° C. for 6 hours. The propanolamine is then distilled off in a water jet vacuum. The distillation residue is mixed with 100 ml of water and extracted four times with 100 ml of ethyl acetate each time. The ester phase is washed with 2N hydrochloric acid and with water and dried over magnesium sulfate. After the ester has been distilled off, 14.1 g of red oil remain (62 90 of theory). In the bulb tube, the oil has a boiling point of 240 to 2500 C at a pressure of 0.02 mbar.

Step 2 A mixture consisting of 8.24 g (86 mmol) 4- (3'-hydroxypropylamino) -3-nitro-anisole from stage 1, 70 ml of benzene and 12 g of anhydrous aluminum chloride is heated to 110 ° C warmed up. After 7 hours the benzene is distilled off. The residue is 40 ml of water are added. The black mass is triturated with 300 ml of 2N sodium hydroxide solution and filtered. The filtrate is extracted with ether and then acidified. From the acidic solution, the product is extracted with ether. After the usual work-up 1.85 g (8.7 mmol) (24% of theory) 4- (3'-hydroxypropylamino) -3-nitro-phenol obtain. The product can be obtained by crystallization from ethyl acetate / petroleum ether getting cleaned. It then melts at 106 to 107 ° C.

CHN Analysis% C% H% N Cg 12 2 ° 4 Calculated: 50.94 5.70 13.20 Found: 50.94 5.66 13.18 Example 5 Preparation of 4- (2'-methylmercaptoethylamino-) 3 -nitrophenol reaction scheme: Stage 1 0.5 g of 4-chloro-3-nitrophenol benzyl ether are heated to 1400 ° C. for 4 hours with 1 ml of 2-methylmercaptoethylamine. After working up as in Example 2 / Stage 1, 0.6 g of an oily reaction product is obtained.

Stage 2 The reaction product from stage 1 is treated with 60% sulfuric acid heated to 80 ° C. After working up as in Example 3 / Stage 2, 0.3 g of the desired reaction product obtained.

CHN analysis% C% H% N C9H12N2 ° 3S calculated: 47.36 5.30 12.27 found: 47.04 5.28 12.20 Example 6 Preparation of 4- (2'-Aminoethylamino -) - 3- nitro-phenol reaction scheme: Stage 1 0.55 g of 4-chloro-3-nitrophenol benzyl ether are heated to 1300 ° C. with 5 ml of 1,2-diaminoethane. After a reaction time of 5 hours, 50 ml of water are added to the batch. The solidly deposited reaction product is filtered off with suction, washed with water and dried. It then melts at 98 ° C.

CHN analysis% C% H% N C15H17N30 calculated: 62.76 5.97 14.63 found: 62.57 5.93 14.53 Stage 2 The reaction product from stage 1 is mixed with 8 ml of 60% strength Sulfuric acid heated to 800 C. After a reaction time of 10 minutes, the batch is with 10 ml of water are added and the pH is adjusted to 7 to 8 with ammonia. the The water phase is extracted with ether. After drying and concentrating the ether phase 0.15 g of solid reaction product remain.

CHNSAnalYe% C% H% N C8H11N303 calculated: 48.73 5.62 21.31 found: 48.50 5.60 21.02 Example 7 Preparation of 4-butylamino-3-nitro-phenol Reaction scheme: Stage 1 0.5 g of 4-chloro-3-nitrophenol benzyl ether are heated to 1400 ° C. with 10 ml of 1-aminobutane in an autoclave. After a reaction time of 6 hours, the 1-aminobutane is distilled off. The distillation residue is taken up in water. The reaction product is extracted with diethyl ether. After the ether has been distilled off, 0.50 g (88% of theory) of 3-nitro-4-butylaminophenol benzyl ether is obtained.

Stage 2 The reaction product from stage 1 is mixed with 10 g of 60% sulfuric acid heated to 800 C. After 10 minutes, the mixture is mixed with 20 ml of water, neutralized with sodium hydrogen carbonate and extracted with diethyl ether.

0.33 g (95% of theory) of a slow one is obtained from the ether phase crystallizing oil. Melts after crystallization from diethyl ether / petroleum ether the reaction product at 800 C.

EXAMPLES OF COSMETIC AGENTS Example 8 Dyeing solution 0.30 g of dye according to Example 6 2.0 g of lauryl alcohol diglycol ether sulfate sodium salt (28% aqueous Solution) 2.0 g ammonia, 25% 95.7 g water 100.0 g blonde natural hair turns 20 Treated for minutes at room temperature with the solution according to Example 8, the solution rinsed with water and dried. The hair is dyed orange-red.

Example 9 Dyeing solution In the solution according to Example 8, the dye according to example 6 replaced by the dye according to example 4. With the received The solution is colored according to Example 8.

An intense, bright red tone is obtained that is free from Is orange or blue.

Because of its special luminosity, the dye is suitable Example 4 primarily for producing highly fashionable hair colors, but in particular also for the production of mixed tones in the red area.

Example 10 Dyeing solution In the solution according to Example 8, the dye replaced by the dye according to Example 3. Then according to example 8 process and obtained an intense red color, which, however, comparatively to Example 9 is less luminous. The dye according to Example 3 is therefore more effective "Natural character" with and is therefore suitable in connection with blue and yellow Nitro dyes for creating natural tones.

Example 11 Oxidation hair colorant in cream form 0.4 g 1,4-diaminobenzene 0.3 g resorcinol 0.3 g dye according to Example 4 0.3 g sodium sulfite, anhydrous 15.0 g of cetyl alcohol 3.5 g of lauryl alcohol diglycol ether sulfate sodium salt (28 96% aqueous Solution) 6.0 g ammonia, 25% strength 74.2 g water 100.0 g 50 g of this hair dye are mixed with 50 ml hydrogen peroxide solution (6%) shortly before use and then applied the mixture to blonde human hair. After a A contact time of 30 minutes at 400 ° C. is rinsed with water and dried. The hair has got an intense mahogany tone.

Example 12 Color stabilizer 0.10 g of the dye according to Example 4 2.00 g of polyvinylpyrrolidone 0.10 g glycerin 40.00 g isopropyl alcohol 57.80 g water 100.00 g white human Hair is inserted into the hairstyle with the setting dye solution and dried. The hair is colored bright red and set.

Claims (10)

Claims 1. A process for the preparation of 4-amino-3-nitro-phenol derivatives of the general formula I. where R represents a straight-chain or branched, unsubstituted or substituted alkyl radical, characterized in that a 4-chloro-3-nitrophenol ether, in particular the methyl, benzyl or t-butyl ether, with a primary alkylamine of the formula H2NR, where R is the has the meaning given above, is converted to the 4- (N-alkylamino) -3-nitrophenol ether and this phenol ether is converted into the 4- (N-alkylamino) -3-nitrophenol of the formula I by acidic ether cleavage. 2. The method according to claim 1, characterized in that the Reaction of the 4-chloro-3-nitrophenol ether with the primary alkylamine at one temperature from 120 to 1500 C. 3. The method according to claim 1 and 2, characterized in that one used as 4-chloro-3-nitrophenol ether 4-chloro-3-nitroanisole and the acidic ether cleavage by boiling with mineral acids or aluminum chloride in benzene. 4. The method according to claim 1 to 3, characterized in that one as primary alkylamFn n-butylamine, 1,2-diaminoethane, 1,3-diaminopropane, 2-dimethylaminoethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, 2-methylmercaptoethylamine, 2-amino-1-butanol, 4-amino-1-butanol, 3-amino-1-butanol, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-amino-1-propanol or 1-amino-2,3-propanediol are used. 5. 4 amino-3-nitrophenol derivatives of the general formula V where R1 is an alkyl radical of the formula CnH (2n + 1) with n = 2-6 or an alkyl radical of the formula ~ (CH2) p ~ U ~ (CH2) q ~ H with U = 0 or S, p = interrupted by a heteroatom 2-3 and q = 2-3 or an alkyl radical of the formula CrH (2r + 1-s) (OH) with r = 3-6 and s = 1-3 which is substituted by one or more OH groups. 6. Means for coloring hair with a dye content and usual cosmetic additives, characterized in that there is at least one 4-amino-3-nitrophenol derivative according to claim 5 contains. 7. Agent for oxidative coloring of hair according to claim 6, in addition containing at least one of the known oxidation hair dyes. 8. Agent according to claim 6 and 7 with a pH of 8.0 to 11.5, by ammonia or organic amines, such as monoethanolamine or triethanolamine, was discontinued. 9. Means in the form of a hair dye with additional Hair fixation according to claim 6, additionally containing known directly in aqueous-alcoholic solution Dyes that are absorbed by the hair and at least one cosmetic polymer. 10. Means according to claim 6 to 9, characterized in that it is the Compounds according to claim 5 in an amount of 0.01 to 4.0% by weight, preferably 0.02 to 2.0% by weight.