DE3250069C2 - Nitroanilines and process for their preparation - Google Patents

Abstract

Nitro-N-(aminoalkyl)aniline derivs. of formula (I) are new. In (I), A is 2-6C alkylene, opt. substd. with OH and/or having -O- or -NH- links in the C chain; R is H or 1-4C alkyl; R' and R'' are H or 1-4C alkyl, hydroxyalkyl or polyhydroxyalkyl; or NR'R'' is a piperidine or morpholine ring; Y is 1-4C alkoxy or NO2, such that when Y is alkoxy, Z is NO2 and para to the amine function, and when Y is alkoxy and A is CH2CH2, R' and R'' are not H, Me or Et; also, when Y is NO2, Z is 1-4C alkoxy or OH para to NO2, and when Z is alkoxy and A is CH2CH2, R' and R'' are not H, Me or Et.

Description

The invention relates to nitroanilines and a method for their production. The nitroanilines according to the invention are for use in coloring agents for keratinische fibers; the latter are in the parent application P 32 37 004 claimed.

It is known to use nitro derivatives of the benzene series the hair a direct fermentation or an additional Give a shimmer in the case of an oxidation dyeing (cf. US-A-3446568).

The Applicant has now found that by means of a special Group of nitroanilines is possible, capillary dyes with a very good stability against weather conditions and washes as well as a good durability against light to achieve.

In particular, these compounds allow the formulations for the capillary coloring a yellow or orange-red tone to rent.  

Besides their remarkable coloring power, the dyes are harmless according to the invention.

These dyes can also be used in oxidation staining agents used to give very shimmering colorations.

Object of the present invention is the provision of new nitroanilines and a process for their preparation.

Other objects of the invention will become apparent from the description and the following examples.

This object is achieved with the present invention.

The invention relates to nitroanilines of the general Formula:

in which mean:
A is an unsubstituted alkylene group, an alkylene group substituted by one or more OH groups, or an alkylene group interrupted by oxygen or by a group -NH-, and wherein alkylene has from 2 to 6 carbon atoms,
R₁ and R₂, which may be identical or different, are hydrogen, C₁-C₄ alkyl, mono- or polyhydroxylated C₁-C₄ alkyl, or R₁ and R₂ with the nitrogen atom to which they are attached, a heterocyclic ring from the group piperidino or can form morpholino,
R is a hydrogen atom or C₁-C₄-alkyl,
Y is C₁-C₄-alkoxy or
NO₂, where

• when Y is alkoxy, Z is NO₂ and is in para position to the amine group, where if Y Methoxy and A represents an ethylene group, R₁ and R₂ are not simultaneously hydrogen,
• - if Y represents NO₂:
  • (A) Z is C₁-C₄-alkoxy or OH and is in para-position to NO₂, wherein when Z is methoxy and A is the ethylene group, R₁ and R₂ can not simultaneously be hydrogen, methyl or ethyl, and
  • (b) when Z represents OH and is para to the amine group, R₁ and R₂ are as defined above.

Under the compounds of general formula (I) fall the compounds of the following general formulas:

Among the above compounds are especially those in which A is an ethylene group, propylene group, Hydroxypropylene group, R is methyl and Y or Z represent methoxy.

Further preferred compounds correspond to the formulas:

The preferred new compounds are the same as above Formula (I), wherein:

A is an alkylene group, an alkylene group substituted by one or more OH groups, or an alkylene group interrupted by a heteroatom such as oxygen, R₁ and R₂ which are identical or different, hydrogen, alkyl, mono- or polyhydroxylated alkyl, or R₁ and R₂ can form a heterocyclic ring from the group piperidino or morpholino,
R is hydrogen or lower alkyl,
Y is alkoxy or NO₂; where:

• when Y is NO₂, A is alkylene, Z is alkoxy and is in para position to NO₂, R₁ and R₂ are not Hydrogen and alkyl,
• - When Y represents NO₂ and Z represents OH and in the para position to NO₂, as well as, if Z means OH and itself in para-position to the amine group, A, R₁ and R₂ has the meanings given above.

In particular:

3- [β- (N, N-diethyl) amino-ethylamino] -4-nitro-anisole,
3- [γ- (N, N-diethyl) aminopropylamino] -4-nitro-anisole,
2- [β- (N, N-diethyl) amino-ethylamino] -5-nitro-anisole,
3- [β-aminoethylamino) -4-nitro-phenol,
2- [β- (N, N-di-β'-hydroxyethyl) aminoethylamino] -5-nitro-anisole,
2- [γ- (N, N-dimethyl) aminopropylamino] -5-nitro-anisole,
3-nitro-4-N, N-dimethylaminoethylamino) -phenol,
3-nitro-4-N, N-di-β-hydroxyethylaminoethylamino) -phenol,
3- [β- (N, N-diethyl) amino-ethylamino] -4-nitro-6-methyl-anisole,
5-nitro-2- [N- (amino-3'-hydroxy-2'-propyl) amino] -anisole,
4-nitro-3- [N- (amino-3'-hydroxy-2'-propyl) amino] -anisole,
2- (β-hydroxy, γ-aminopropylamino) -5-nitroanisole,
3- (β-hydroxy, γ-aminopropylamino) -4-nitroanisole,

this list should not be limiting.  

The compounds particularly preferred according to the invention represent compounds of formula (IB) which are excellent Stability to weathering and washes as well as a very good durability against light own and allow the coloring of yellow nuances. also the compounds of the formula (IC) are also very far interesting, as they allow orange-red dyeings, where these against the effects of light, weather conditions as well are very resistant to shampooing.

These compounds also have the advantage that they are largely harmless.

The compounds of the formula (IA) are obtained by Reaction of amines of the formula

with 3-alkoxy-4-methoxy-nitrobenzene or with 3-alkoxy-4-chloro-nitrobenzene. They can also be obtained by condensation a halogen derivative of the formula

with benzene or para-toluenesulfonamide, which is obtained is by reaction of benzene or para-Toluolsulfochlorid with 2-amino-5-nitro-1-alcoxy-benzene followed by acid hydrolysis of the substituted sulfonamide follows.  

The compounds of formula (IB) are obtained by Reaction of amines of the following formula:

with 2-methoxy-4-alcoxy-nitrobenzene or with 2-chloro-4-alcoxy-nitrobenzene.

When R₁ and R₂ are alkyl, the compounds of formula (IB) can also be obtained by condensation of halogen derivatives

with 2-arylsulfonylamino-4-alcoxy-nitrobenzene, followed by a Acid hydrolysis of the resulting substituted sulfonamides follows.

The compounds of formula (IC) can be prepared from halogen derivatives of the general formula

wherein X represents a halogen atom, such as chlorine or bromine, either by reaction of the halogenated derivative of the formula (III) with an amine

where R₁ and R₂ have the meanings given above, or when the aminoalkyl substituent of the aromatic amino group in ortho position to the NO₂ group has a primary amine (R₁ and R₂ are hydrogen), by reaction of potassium phthalimide with a halogen compound of the formula (III) and subsequent Treatment of the substituted obtained in this way Phthalimide with hydrazine (Gabriel reaction).

The compounds of the formula (III) in which A is ethylene, and X represents bromine can be easily converted by reaction of hydrobromic acid with N-2-nitro-4-hydroxy-phenyl) oxazolidin-1,3-one-2 to be obtained, the latter is produced by the action of dilute sodium hydroxide solution at room temperature on β-chloroethyl-N- (2-nitro-4-hydroxyphenyl) carbamate, which in the third step of Example 1 is described in FR-PS 2,348,911.

The compounds of the formula (ID) and (IE) are especially obtained by reacting an amine of the formula NH₂CH₂-CHOH-CH₂NH₂ with alkoxy-3-methoxy-4-nitrobenzene or with methoxy-2-alcoxy-4-nitrobenzene.

Those produced using the nitroanilines of the invention medium contained in a cosmetically acceptable solvent at least a compound according to formula (I) and can be used for direct staining of keratin fibers or for oxidation staining these fibers are used, wherein in the latter case the compounds of the formula (I) of the basic color, which by oxidative development of a precursor an oxidation dye has been obtained, an additional Give a shimmer.

These agents contain the compounds of the invention in proportions between 0.001 and 5 wt .-%, preferably between 0.01 and 3 wt .-%, based on the total weight of  Colorant.

They can be anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof, preferably cationic and / or nonionic surfactants contain. These surface-active products are in the Agents according to the invention in proportions between 0.5 and 55 wt .-%, preferably between 2 and 40 wt .-%, based on the total weight of the remedy, before.

In the colorants, the vehicle generally becomes formed by water and it can also be organic Solvent is added to solubilize compounds, not sufficiently soluble in water are. Among the solvents are: low alkanols, such as ethanol and isopropanol, polyols, such as glycerol, glycols or glycol ethers, such as butoxy-2-ethanol, ethylene glycol, Ethylene glycol monoethyl ether, propylene glycol, diethylene glycol monoethyl ether and monomethyl ether, as well as analogous products and their mixtures. These solvents are preferably in proportions of from 1 to 75% by weight, in particular from 5 to 50 wt .-%, based on the total weight of the agent before.

The agents can be thickened, preferably with compounds from the group sodium alginate, Gum arabic, cellulose derivatives, such as methylcellulose, Hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and various polymers which are thickening Function, in particular acrylic acid derivatives. It is also possible to use mineral thickeners, like bentonite. These thickeners are preferably in proportions between 0.5 and 10 wt .-%, in particular between 0.5 and 3 wt .-%, based on the total weight the remedy, before.  

The funds can also be different Excipients, as they usually in dyes used for hair, in particular penetrating agents, Sequestering agents, film-forming agents, buffers, Perfumes, alkalizing and acidifying agents. These funds can be in various forms, e.g. B. as Liquid, cream, gel or any other suitable form, to carry out the coloring of the hair. You can also conditioned in aerosol bottles in the presence of a propellant his.

The pH of these colorants may be between 3 and 11.5, preferably between 5 and 11.5. You put the desired pH with the aid of an alkalizing agent, such as z. Ammonia, sodium, potassium or ammonium carbonate, sodium or potassium hydroxide, alkanolamines such as mono-, di- or triethanolamine, amino-2-methyl-2-propanol or amino-2-methyl-2-propanediol-1,3, Alkylamines, such as ethylamine, diethylamine or triethylamine, or with the aid of an acidulant, such as phosphoric acid, hydrochloric acid, tartaric acid, acetic acid, Lactic acid or citric acid.

If the means of direct dyeing The hairs are determined, they can according to the compounds the invention contain further direct dyes, such as azo dyes, anthraquinone dyes, such as. B. tetraaminoanthraquinone, Aminoquinones, nitro dyes of the benzene series, which differ from the compounds of formula (I); in particular the following compounds:

3-nitro-4-amino-6-chloro-N-β-aminoethylanilin,
3-nitro-4-N'-methylamino-N-β-aminoethylanilin,
3-nitro-4-amino-N-β-hydroxyethylaniline,
4- (3-nitro-4-n-β-hydroxyethylamino-phenoxyethanol,
3-nitro-4-N'-β-aminoethylamino-N- (di-β-hydroxyethyl) aniline,
3-nitro-4-N-β-hydroxyethylamino-6-chloro-aniline,
3-nitro-4-amino-6-methyl-N-β-hydroxyethylaniline,
N, N'-di-β-hydroxyethyl-4-nitro-orthophenylenediamine,
2-nitro-N-β-aminoethylanilin,
2-methyl-6-nitro-aniline
3-nitro-4-amino-phenol,
3-nitro-4-β-hydroxyethylamino-phenol,
3-nitro-4-amino-6-methyl-phenol,
3-Amino-4-nitro-phenol,
2-amino-3-nitro-phenol,
3-nitro-6-N-β-hydroxyethylamino-anisole,
3- (N-β, γ-dihydroxypropylamino) -4-nitro-4-anisole,
3-N-methylamino-4-nitro-phenyl-β, γ-dihydroxypropyl ether,
N, N'-di (β-hydroxyethyl) -p-phenylenediamine,
3-nitro-4-N'-methylamino-N, N- (di-β-hydroxyethyl) aniline.

The concentrations of these direct dyes differing from distinguish the dyes according to the formula (I), may be between 0.001 and 5% by weight, based on the total weight of the agent.

These remedies are based on the keratinic fibers for one Planned from 5 to 70 minutes, then the Rinsed fibers, possibly washed, rinsed again and dried.

The remedies can also be used as capillary lotion be used to insert the hair or the water wave, on the one hand to give the hair a slight coloring, and on the other hand the water wave to an improved grip give. In this case they are in the form of aqueous, alcoholic or aqueous-alcoholic solution and contain at least a cosmetic resin. Their application takes place on the moist, previously washed and rinsed hair, optionally be inserted and then dried.  

The cationic resins used in the water lotions may in particular represent: polyvinylpyrrolidone, copolymers of crotonic acid vinyl acetate, vinyl pyrrolidone vinyl acetate, Copolymer monoesters of maleic anhydride butyl vinyl ether, Maleic anhydride methyl vinyl ether and all others cationic, anionic, nonionic or amphoteric Polymers commonly used in this type of agents become. The cosmetic resins are in the remedies according to the invention in proportions of 1 to 3 wt .-%, preferably from 1 to 2% by weight, based on the total weight of the Means before.

If the agents form oxidation dyes, the Compounds of formula (I) according to the invention in essentially used to make the final stain a shimmer to rent.

These remedies then contain in combination with at least a nitro dye of the formula (I) precursors of oxidation dyes.

You can z. B. include: Paraphenylenediamines, such as paraphenylenediamine, Partoluylenediamine, 2,6-dimethyl-paraphenylenediamine, 6-dimethyl-3-methoxy-paraphenylenediamine, N- (β-methoxyethyl) -paraphenylenediamine, 4- (N, N-di-β-hydroxyethylamino) aniline, 4- (N, N-ethyl-carbamylmethylamino) -aniline, and their Salts.

You may also contain para-aminophenols, such as. B .: Para-aminophenol, N-methyl-para-aminophenol, 2-chloro-4-amino-phenol, 3-chloro-4-amino-phenol, 2-methyl-4-amino-phenol and their salts.

They may also contain heterocyclic derivatives, for. B. 2,5-diaminopyridine, 7-aminobenzomorpholine.  

The funds can be combined with Precursors of oxidation dyes containing coupling agents, as known in the art.

Coupling substances which may be mentioned in particular are: metadiphenols, such as resorcinol, 2-methyl-resorcinol, metaaminophenols, such as Metaaminophenol, 2-methyl-5-amino-phenol, 2-methyl-N-β-hydroxyethyl-5-amino-phenol, 6-hydroxybenzomorpholine and their salts, metaphenylenediamines, such as 2,4-diaminophenoxyethanol, 2,4-diaminophenyl-β-hydroxypropyl ether, 6-aminobenzomorpholine, 2- (N-β-hydroxyethylamino) -4-aminophenoxyethanol, 2,4-diaminophenyl-β, γ-dihydroxypropyl ether and salts thereof, Metaacylaminophenols, Metaureidophenols, Metacarbalocoxyaminophenols, such as 2-methyl-5-acetylamino-phenol, 2-methyl-5-ureido-phenol, 2-methyl-5-carbethoxyamino-phenol.

As another, to be used in the funds Coupling agents are: α-naphthol, coupling agents, which have an active methylene group, such as diketone compounds, Pyrazolones and heterocyclic coupling agents, such as 2,4-diaminopyridine, as well as their salts.

These agents contain except the precursors of the oxidation dyes reducing agents and / or antioxidants, in particular sodium sulfite, thioglycolic acid, thiolactic acid, Sodium bisulfite, ascorbic acid and hydroquinone. These Agents are in proportions between 0.05 and 1.5 wt .-%, based on the total weight of the remedy, before. The precursors of Oxidizing dyes may be used in the compositions according to the invention in concentrations between 0.001 and 5 wt .-% and preferably between 0.03 and 2 wt .-%, based on the total weight of the agent. The coupling substances may also be present in amounts between 0.001 and 5% by weight, preferably between 0.015 and 2 wt .-%, based on the Total weight of the agent are present. Your pH is  preferably between 7 and 11.5 and is using the set above alkalizing agent.

The process for dyeing keratinic fibers, in particular human hair, under development with the aid of an oxidizing agent, consists in applying the colorant on the Hair, wherein the agent on the one hand a dye of the invention and dye precursors, and in development staining with the aid of an oxidizing agent, which is present in the colorant, or which is in a second step is applied to the hair.

The oxidizing agent is preferably selected from the group hydrogen peroxide, Urea peroxides and persalts selected. In particular, a hydrogen peroxide solution is used with 20 volumes.

Once the agent with the oxidizing agent on the applied keratinischen fibers, one lets 10 to 50 Minutes, preferably 15 to 30 minutes, then rinses the keratinic fibers, washing them if necessary with a shampoo, she washes again and dry them.

The following examples are intended to explain the invention in more detail, without limiting it.  

example 1 Preparation of 3- (β-N, N-diethylaminoethylamino-4-nitroanisole hydrochloride

0.25 mol (46 g) of 2,4-dimethoxy-nitrobenzene are added in 140 ml N, N-diethylethylenediamine and then warms the reaction mixture 4 hours at 110 ° C. After cooling, pour this in 1,500 kg of ice water. You extract the desired Product by means of ethyl acetate. To the with the help of Sodium sulfate dried ethyl acetate solution, which then auf Is cooled 0 ° C, are added with stirring 50 ml with hydrogen chloride gas saturated ethanol. In this case, the 3-β-N, N-diethylaminoethylamino-4-nitro-anisole hydrochloride falls out. This is centrifuged off, washed with ethanol and extracted Recrystallized ethanol. After drying in vacuo It melts at 157 ° C.

Example 2 Preparation of 3-γ-N, N-dimethylaminopropylamino-4-nitroanisole hydrochloride

Add 0.05 mol (9.15 g) of 3,4-dimethoxy-nitrobenzene to 30 ml N, N-dimethylpropylenediamine and then heated the reaction mixture 4 hours at 110 ° C.  

After cooling, this is poured into 300 g of ice water and extracted with ethyl acetate, the precipitated oil. After this Dry over sodium sulfate to the ethyl acetate phase, the cooled to 0 ° C, 10 ml saturated with hydrogen chloride gas Ethanol added.

3- (γ-N, N- dimethylaminopropylamino-4-nitro-anisole hydrochloride falls out. This is centrifuged off, with Ethanol and recrystallized from ethanol. After this Drying in vacuo melts with decomposition at 204 ° C.

Example 3 Preparation of 2- (β-N, N-diethylaminoethylamino) -5-nitroanisole hydrochloride

0.05 mol (9.15 g) of 3,4-dimethoxy-nitrobenzene is added 30 ml of N, N-diethylethylenediamine and the solution is warmed 15 hours at 110 ° C. The cooled reaction mixture is then poured into 300 g of ice water. That in the form of the free Base desired product precipitates as an oil, which one with Extracted ethyl acetate. The ethyl acetate is in vacuo evaporated. The remaining oil is dissolved in 15 ml of absolute ethanol dissolved. After addition of 10 ml of absolute ethanol, which is saturated with hydrogen chloride gas, obtained a precipitate of 2- (β-N, N-diethylaminoethylamino-5-nitroanisole hydrochloride, which after recrystallization  from ethanol at 85 ° C and drying in vacuo at 60 ° C. with decomposition at 230 ° C melts.

Example 4 Preparation of β-aminoethylamino-3-nitro-4-phenol hydrochloride

0.432 mol (75 g) of 3-chloro-4-nitrophenol are added 282 ml of ethylenediamine and then heated the reaction mixture 13 hours on the boiling water bath. The cooled The solution is then poured into 2.6 l of ice-water containing 1.09 l of hydrochloric acid (d = 1.18) were added, poured. After cooling to -10 ° C for several hours, the 3- (β-aminoethyl-amino-4-nitro-phenol hydrochloride crystallizes. This is centrifuged off, with a 2N iced hydrochloric acid solution and then washed with ethanol. After recrystallization from water melts the dried product with decomposition at a Temperature over 260 ° C.

Example 5 Preparation of 2- (β-N, N-di-β-hydroxyethylaminoethylamino-5-nitroanisole hydrochloride First step Preparation of 2- (N-benzenesulfonyl, N-β-bromoethylamino) -5-nitroanisole

This compound is obtained by adding in dimethylformamide at about 80 ° C dibromo-1,2-ethane with the calcium salt of 2-N-benzenesulfonylamino-5-nitro-anisole according to the FR-PS 1 491 617. This product melts at 122 ° C.

Second step Preparation of 2- (N-bromoethylamino) -2-5-nitroanisole

169 g (0.407 mol) of substituted benzenesulfonamide, which obtained after the above step, after and after stirring in 500 ml of 96% sulfuric acid, wherein during the whole process the temperature is between 15 to 20 ° C stops. In the further one keeps the reaction mixture 1 h at this temperature and then pour this over 3 kg crushed ice. The precipitated crystallized product is centrifuged off, washed with water and in vacuo dried at 60 ° C. It melts at 118 ° C.

Third step Preparation of 2- (β-N, N-di-β'-hydroxyethylaminoethylamino) -5-nitroanisole hydrochloride

To 110.4 g (1.05 mol) of diethanolamine, which was previously heated to ca. 100 ° C had been heated, one gradually, within of 25 minutes and with stirring, 41.3 g (0.15 mol) of 2- (N-β-bromoethylamino) -5-nitro-5-anisole. After 1½ hours of warming to about 100 ° C, the reaction mixture is poured into 400 g of ice-cooled 1N sodium hydroxide, and then extract the desired product with ethyl acetate. Evaporate the ethyl acetate in a vacuum. The remaining orange oil is in  Dissolved 120 ml of absolute alcohol. After addition of 50 ml absolute ethanol saturated with hydrogen chloride gas when a precipitate of 2- (β-N, N-di-β-hydroxyethylaminoethylamino) -5-nitroanisole hydrochloride is obtained, which after recrystallization from alcohol at 90 ° C and drying in vacuo at 60 ° C over potassium hydroxide with decomposition between 168 and 170 ° C melts.

Example 6 Preparation of 2- (γ-N, N-dimethylaminopropylamino) -5-nitroanisole hydrochloride

0.4 mole (73.2 g) of 3,4-dimethoxy-nitrobenzene is added in 220 ml N, N-dimethylpropylenediamine and the solution is heated for 12 h 115 ° C. The cooled mixture is then poured into 2.2 kg of ice water cast. The product desired in the state of a free base precipitates in the form of an oil, which is extracted with ethyl acetate extracted. Then the ethyl acetate is evaporated in vacuo. The remaining red oil is dissolved in 100 ml of absolute ethanol dissolved. After addition of 100 ml of absolute ethanol, which is saturated with hydrogen chloride gas, a precipitate is obtained of 2- (γ-N, N-dimethylaminopropylamino-5-nitroanisole hydrochloride, which after recrystallization from absolute Ethanol and drying in vacuo at 80 ° C with decomposition melts at 181 ° C.

Example 7 Preparation of 3-nitro-4-N, N-dimethylaminoethylamino-phenol First step Preparation of N- (2-nitro-4-hydroxy-phenyl) oxazolidine-1,3- on-2

0.02 mol (5.2 g) of β-chloroethyl-N- (2-nitro- 4-hydroxyphenyl) carbamate (obtained according to that in Example 1 from FR-PS 2,348,911) in 17 ml of 2.36N Sodium hydroxide solution of 20 ° C. After completion the addition is kept the reaction mixture for 30 minutes long at 20 ° C, then diluted with 20 ml of water and neutralized it at 0 ° C with the aid of a hydrochloric acid solution. The wished Product fails. This is centrifuged off, with water washed and recrystallized from ethanol. It melts 170 ° C.

Second step Preparation of 3-nitro-4-β-bromoethylamino-phenol

To 375 ml of 48% hydrochloric acid, which previously heated to 90 ° C. is added within 10 minutes with stirring 0.55 mole (125 g) of N- (2-nitro-4-hydroxy-phenyl) oxazolidin-1,3-one-2. The reaction mixture is held for 30 minutes 90 ° C and then filtered warm. After cooling the filtrate precipitate the desired product in the form of hydrobromide. The hydrobromide is centrifuged off, with stirring in 500 ml Water added to the 3-nitro-4-β-bromoethylamino-phenol  to be released, which is centrifuged off, washed with water and dried in vacuo. After recrystallization Benzene melts the product at 122 ° C.

Third step Preparation of 3-nitro-4-N, N-dimethylaminoethylamino-phenol

The mixture is heated for 20 minutes at 60 ° C 0.0766 mol (20 g) of 3-nitro 4-β-bromoethylamino-phenol in 60 ml of an aqueous 40% Dimethylamine. Then pour the reaction mixture into 300 ml of ice-water and neutralized with acetic acid. The desired product fails. It is centrifuged, washed with water and recrystallized from ethanol. To drying in vacuo, it melts at 151 ° C.

Example 8 Preparation of 3-nitro-4-N, N-di-β-hydroxyethylaminoethyl amino-phenol

5.2 g (0.02 mol) of 3-nitro-4-N-β-bromoethyl-amino-phenol are kept for 1 h in 20 ml of diethanolamine at 60 ° C. Then pour the reaction mixture in 100 g of ice water and neutralized the solution with acetic acid. After leaving for a Night at 0 ° C centrifuged the desired product, which failed, from. After washing with a little ice water and dried in vacuo, the product is ethyl acetate recrystallized. It melts at 115 ° C.

Example 9 Preparation of 3- (β-N, N-diethylaminoethylamino) -4-nitro 6-methyl-anisole First step Preparation of 3- (N-p-toluenesulfonylamino) -4-nitro-4- 6-methyl-anisole

To a solution of 0.058 mol (10.6 g) of 3-amino-4-nitro-6-methylanisole In 60 ml of pyridine are added gradually with stirring at a temperature between 50 and 55 ° C 0.096 moles (18.3 g) Paratoluolsulfochlorid. After three hours of heating at one Temperature between 50 and 55 ° C is poured into the reaction mixture in 300 ml of ice-water. The desired product, which precipitates, is centrifuged, washed with water and recrystallized from dimethylformamide. It melts at 211 ° C.

Second step Preparation of 3- (N-p-toluenesulfonyl-N-β-diethylaminoethyl amino) -4-nitro-6-methyl-anisole

The mixture is heated while stirring on the boiling water 0.0353 mol (11.9 g) 3- (N-p-toluenesulfonylamino) -4-nitro-6-methylanisole in 50 ml of dimethylformamide, to which 2.8 g of quicklime was added are. Then, gradually added 0.075 mol (10.2 g) of 2-N, N-di ethylamino-1-chloro-ethane too. After 3 hours of heating the reaction mixture is poured into 200 ml of ice water. The desired product crystallizes slowly. It is centrifuged, washed with water. After drying it will  recrystallized from ethanol. It melts at 114 ° C.

Third step Preparation of 3- (β-N, N-diethylaminoethylamino) -4-nitro 6-methyl-anisole

0.021 mole (9.3 g) of substituted paratoluene sulfonamide, which has been obtained according to the above step, are gradually added with stirring to 25 ml of 96% sulfuric acid added, keeping the whole at a temperature between 7 and 10 ° C holds. Stirring is complete after completion of the addition continue for 5 h at room temperature and then pour the reaction mixture in 200 ml of ice-water.

While cooling, the reaction mixture is washed with 10 N sodium hydroxide solution alkalized; the desired product falls in the form of an oil, which crystallizes quickly. The product is centrifuged off, washed with water, dried and recrystallized in hexane. It melts 70 ° C.

Example 10 Preparation of 2- (β-hydroxy-γ-aminopropylamino) -5-nitro- anisole

0.0164 mole (3 g) of 3,4-dimethoxy-nitrobenzene are added 0.177 moles (16 g) of 1,3-diamino-2-propanol and warms the mixture For 4 h at 100 to 110 ° C. After cooling, pour the reaction mixture in 90 ml of water; then centrifuged (essore) and wash the desired product, which as free base fails, with water. This product is about 40 ml  Add 2N hydrochloric acid solution. Centrifuged after stirring for 30 minutes the 2-β-hydroxy-γ-aminopropylamino-5-nitroanisole hydrochloride and wash it with alcohol. After recrystallization from water it melts at 227 ° C.

Example 11 Preparation of 3-β-hydroxy-γ-aminopropylamino-4-nitro- anisole

0.0218 mol (4 g) of 2,4-dimethoxy-nitrobenzene are added 0.177 moles (16 g) of 1,3-diamino-2-propanol and heats the Mixture for 3 h at a temperature between 100 and 110 ° C. After cooling, pour the reaction mixture in 60 ml of water. The desired product fails. It is centrifuged off, washed with water and treated while stirring with 40 ml of 2N hydrochloric acid. The 3- (β-hydroxy γ-amino-propylamino) -4-nitroanisole hydrochloride is centrifuged off and washed with absolute alcohol.  3 g of the abovementioned hydrochloride are dissolved in 90 ml dissolved boiling water. It is filtered in the heat, to to remove a slight insoluble precipitate, alkalized then the filtrate with concentrated ammonia.

The 3- (β-hydroxy-γ-aminopropylamino) -4-nitroanisole, which precipitates, is centrifuged off, washed with water and in Vacuum dried. It melts at 178 ° C.

Application example 1

The following colorant is produced:

3-γ-dimethylaminopropylamino-4-nitroanisole HCl | 2 g 3-nitro-4-amino-6-chloro-N-β-aminoethylanilin hydrochloride 0.6 g 3-nitro-4-N'-methylamino-N-β-aminoethylanilin dihydrobromide 0.515 g Cellosize WP 03 2 g Cetyldimethylhydroxyethylammonium chloride 2 g Ammonia, D = 1.18 (22 ° B) 2.5 g Water up 100 g pH 8.5

This mixture gives 25 minutes exposure to 30 ° C on naturally light chestnut hair after rinsing and shampooing them a dark chestnut brown Color with coppery shimmer.  

Application Example 2

The following colorant is produced:

2- (N-γ-dimethylaminopropylamino) -5-nitroanisole hydrochloride | 0.6 g 3-nitro-4-N-β-hydroxyethylamino-phenol 0.25 g 3-nitro-4-amino-N-β-hydroxyethylaniline 0.26 g 2-N-β-hydroxyethylamino-5- (4-N, N-di-β-hydroxyethylamino-anilino) -1,4 -benzoquinone 0.3 g 2-butoxyethanol 10 g Cemulsol NP 4 12 g Cemulsol NP 9 15 g Oleic alcohol, oxyethylated with 2 moles of ethylene oxide 1.5 g Oleic alcohol, oxyethylated with 4 moles of ethylene oxide 1.5 g aqueous solution of triethanolamine (20%) 1 g Water up 100 g pH 8.7

This mixture gives 30 minutes exposure to 30 ° C on up to 90% natural white hair after rinsing and Shampooing it a bright red color.

Application example 3

The following composition is prepared:

3- (N-β-aminoethylamino) -4-nitroanisole HCl 0.4 g 3-nitro-4-N-β-hydroxyethylamino-phenoxy-ethanol 0.5 g 3-nitro-4-N'-methylamino-N-β-aminoethyl-amino dihydrobromide 0.63 g 2-butoxyethanol 6 g Lauramid 1.5 g lauric acid 1 g   hydroxyethyl 5 g Monoethanolamine 2 g Water up 100 g pH 10

This mixture gives 20 minutes exposure to 25 ° C on hair discolored to whitening after rinsing and shampooing it a red-copper maroon Coloring.  

Application Example 4

The following colorant is produced:

3-β-Diethylaminoethylamino-4-nitroanisole hydrochloride | 0.26 g tetraaminoanthraquinone 0.3 g 3-nitro-4-amino-6-methyl-N-β-hydroxyethyl-aniline 0.15 g propylene glycol 10 g Carbopol 934 2 g Ammonia, D = 1.18 (22 ° B) 4 g Water up 100 g pH 5.8

This mixture gives 30 minutes exposure to 28 ° C on hair discolored to whitening after rinsing and shampooing it a golden blonde color.

Application Example 5 3-β-diethylaminoethylamino-4-nitroanisole hydrochloride | 1 g Ethanol at 96 ° 10 g Alfol C₁₆ / ₁₈ 8 g Lanette wax E 0.5 g Cemulsol B 1 g Oleindiethanolamid 1.5 g Aqueous solution of monoethanolamine with 20% 0.5 g Water up 100 g pH 7.7

On discolored hair: 7 Y 8/9
On 90% natural white hair: 7 Y 6.5 / 6

Application Example 6 2- (β-N, N-di-β'-hydroxyethylaminoethylamino) -5-nitroanisole hydrochloride | 2 g 2-butoxyethanol 10 g hydroxyethyl 2 g Cetyldimethylhydroxyethylammoniumchlorid 2 g Aqueous solution of monoethanolamine with 20% 2.5 g Water up 100 g pH 9

On discolored hair: 7.5 Y 8/13
On up to 90% natural white hair: 7.5 Y 6/8

Application example 7

The following colorant is produced:

3-nitro-4-N, N-di-β-hydroxyethylaminoethylamino-phenol | 0.41 g 3-N, N-dimethylaminoethylamino-4-nitroanisole, monohydrochloride 1.34 g 3-nitro-4-N'-β-aminoethylamino-N, N-di-β-hydroxyethylaniline-dihydrochloride 0.26 g 3-nitro-3-4-amino-6-methyl-N-β-hydroxyethyl-aniline 0.1 g Cellosize WPO3 2 g Cetyidimethyl-hydroxyethyl ammonium chloride 2 g 5% ammoniacal solution 5 g Water up 100 g pH 8

This mixture gives 15 minutes exposure 30 ° C on 90% natural white hair after rinsing and shampoo a coppery mid-maroon Coloring.  

Application Example 8

The following colorant is produced:

3-β-N, N-diethylaminoethylamino-4-nitro-6-methylanisole | 0.15 g 3- (4-nitro-N-β-hydroxyethylamino) phenyl-β-hydroxypropyl ether 0.10 g 3-nitro-4-N'-β'-aminoethylamino-N, N-di-β-hydroxyethylaniline dihydrochloride 0.135 g Butoxy-2-ethanol 10 g Diethanolamides of Coprah fatty acids 2.2 g lauric acid 0.8 g ethylene glycol 2 g Monoethanolamine 1 g Water up 100 g pH 7

This mixture results in 30 minutes exposure 30 ° C on discolored hair this after rinsing and Shampooing a hazelnut brown dye.  

Application Example 9

The following colorant is produced:

2- (β-hydroxy-γ-aminopropylamino) -5-nitroanisole hydrochloride | 0.3 g 3-nitro-4-N-β-hydroxyethylamino-phenol 0.2 g 3-nitro-4-N'-methylamino-N, N-di-β-hydroxyethylenanilin 0.5 g propylene glycol 10 g hydroxyethyl 2 g Cetyldimethylhydroxyethylammoniumchlorid 2 g Triethanolamine solution with 20% 1 g Water up 100 g pH 7.6

This mixture gives 30 minutes exposure 30 ° C on 90% natural white hair after the same rinsing and shampooing a coppery blonde dye.  

The trade names used in the examples designate the following products:

Cemulsol NP 4 Nonylphenol with 4 moles of ethylene oxide, available from Rhôhe Poulenc Cemulsol NP 9 Nonylphenol with 9 moles of ethylene oxide, available from Poulenc Cellosize WPO 3 Hydroxyethylcellulose, available from Union Carbide Lauramid Monoethanolamide of lauric acid, available from Witco Alfol C₁₆ / ₁₈ Cetylstearyl alcohol, available from Cond'a Lanette wax E partially sulfated cetylstearyl alcohol, available from Henkel Cemulsol B ethoxylated castor oil, available from Rhône Poulenc Carbopol 934 Acrylic acid polymer having a molecular weight of 2 to 3 million, available from Goodrich Chemical Company

Claims (5)

1. Nitroanilines of the general formula: in which mean
A is an unsubstituted alkylene group, an alkylene group substituted by one or more OH groups, or an alkylene group interrupted by oxygen or by a group -NH-, and wherein alkylene has from 2 to 6 carbon atoms,
R₁ and R₂, which may be identical or different, are hydrogen, C₁-C₄ alkyl, mono- or polyhydroxylated C₁-C₄ alkyl, or R₁ and R₂ with the nitrogen atom to which they are attached, a heterocyclic ring from the group piperidino or can form morpholino,
R is a hydrogen atom or C₁-C₄-alkyl,
Y is C₁-C₄-alkoxy or
NO₂, where

• when Y is alkoxy, Z is NO₂ and is para to the amine group, where when Y is methoxy and A is ethylene, R₁ and R₂ are not simultaneously hydrogen,
• - if Y represents NO₂:
  • (A) Z is C₁-C₄-alkoxy or OH and is in para-position to NO₂, wherein when Z is methoxy and A is the ethylene group, R₁ and R₂ can not simultaneously be hydrogen, methyl or ethyl, and
  • (b) when Z represents OH and is para to the amine group, R₁ and R₂ are as defined above.

2. A process for the preparation of compound according to claim 1, wherein Y is OCH₃, Z is NO₂ and is in the para position to the amine group, characterized in that in a conventional manner an amine of the formula: with alkoxy-3-methoxy-4-nitrobenzene or with alkoxy-3-chloro-4-nitrobenzene, or a condensation of a halogen derivative of the formula: wherein X represents a halogen atom, with benzene or para-toluenesulfonamide and then performs an acid hydrolysis. 3. A process for the preparation of the compounds according to claim 1, wherein Y is NO₂, Z is alkoxy or OH and is in para-position to NO₂, characterized in that in a conventional manner an amine of the formula with methoxy-2-alkoxy-4-nitrobenzene or with chloro-2-alkoxy-4-nitrobenzene, or when R₁ and R₂ are alkyl, a condensation of a halogen derivative of the formula with arylsulfonylamino-2-alkoxy-4-nitrobenzenes, followed by acid hydrolysis of the resulting substituted sulfonamides. 4. A process for the preparation of the compounds according to claim 1, wherein Z is OH and is para to the amine group, characterized in that starting from halogen derivatives of the formula (III): in which X represents a halogen atom and reacts these in a manner known per se with one of the following compounds:

• (1) an amine of the formula or
• (2) when R₁ and R₂ are hydrogen, with potassium phthalimide and then treating the substituted phthalimide with hydrazine.

5. Process for the preparation of the compounds characterized in that reacting in a conventional manner, an amine of the formula N₂N-CH₂CHOH-NH₂ with alkoxy-3-methoxy-4-nitrobenzene or with methoxy-2-alkoxy-4-nitrobenzene.