NL9400122A - Novel derivatives from the benzene series, method of preparing them, and use thereof to dye keratin fibres - Google Patents

Abstract

The invention relates to novel nitro derivatives from the benzene series, viz. (3-nitro-N-β-hydroxyethyl-4- amino)phenoxyethanol and (3-nitro-N-β-hydroxyethyl-4- amino)phenyl β,γ-dihydroxypropyl ether, which can be used to dye keratin fibres, in particular human hair. The two compounds just mentioned can be used in dye preparations together with nitro-p-phenylenediamines, said preparations being suitable for direct dyeing or for oxidative dyeing of keratin fibres.

Description

New derivatives of the benzene series, their preparation method and their use for dyeing keratin fibers.

The invention relates to new benzene series nitro derivatives, their use in dyeing keratinous fibers and in particular human hair and to their preparation.

As is known, hair is often given a direct color or a complementary appearance in oxidation paints by using benzene series nitro derivatives. It has already been recommended to use such nitro-p-phenylenediamines, especially nitro-p-phenylenediamines, both for direct paints and for oxidation paints.

However, the good usability of nitro-p-phenylenediamine has been questioned in recent years and efforts have therefore been made to replace this dye in hair dye preparations. Nitro-p-phenylenediamine is often used in capillary paint for the composition of warm nuances such as mahogany, chestnut with more or less red copper sheen, so that it is necessary for such preparations to find other direct dyes that can impart red nuances to keratin fibers. New nitro-p-phenylenediamines have now been found which can provide the red in capillary paint formulations.

It has also been found that the capillary paints thus obtained with the aid of this new dye class have good washability and light resistance.

Moreover, these dyes have the great advantage that they have a good shelf life in the carriers usually used in oxidation paint preparations, in particular in alkaline medium in the presence of reducing agents, so that they can be combined with said oxidation dyes to obtain rich nuances and reflection.

The present invention therefore relates to novel nitro-p-phenylenediamines and their preparation methods.

The invention also relates to these nitro-p-phenylenediamine-containing dyeing preparations for keratinous fibers and in particular human hair, which can be used for direct dyeing of the hair or for dyeing along oxidative veg.

The nitro-p-phenylenediamines of the invention have the general formula 1. wherein an alkyl radical, a mono or polyhydroxyalkyl radical or an aminoalkyl radical, the amino group of which may optionally be mono- or disubstituted with an alkyl radical, and R1 represents an alkyl radical. In addition, the cosmetically acceptable salts of these compounds are included in the invention included.

In formula 1, an alkyl radical is preferably a radical of 1 to U carbon atoms.

Particularly preferred groups; for R ^ methyl, ethyl, n-propyl, B-hydroxyethyl, B-hydroxypropyl Βγ-dihydroxypropyl, N, N-diethylaminoethyl, 0-aminoethyl9 γ-hydroxy-j propyl and γ-aminopropyl and for Rg methyl, ethyl, propyl and isopropyl.

Compounds which deserve the particular front door have the formula 2, wherein R * 1 represents a mono or polyhydroxyalkyl radical or an aminoalkyl radical, the amino group of which may be mono- or digi-substituted with an alkyl radical and R 9 represents alkyl , suggests.

These compounds have good paint properties and stability and are particularly harmless.

Particularly remarkable results have been obtained! 1 contains the compounds of the formula II, wherein R 1 and R g are respective have the following meanings:

The invention also relates to the preparation of the compounds of the formula 1. These compounds can be prepared by direct reaction of haloalkanes of the formula RjX, wherein X represents halogen and Rj the above; has the meaning or an alkyl sulfate, such as methyl sulfate or! ethyl sulfate, with the 2-alkyl-5-nitro-p-phenylenediamine, e.g. image in water-alcohol medium, under reflux, in the presence of alkali or alkaline earth metal carbonate. !

Another process may be to react haloalkanes of the formula XRj (wherein X and Rj have the above meanings) or alkyl sulfates with the 3-alkyl, N-arylsulfonyl-4-amino-6-nitroanilines and hydrolyze the thus obtained sulfonamides. j

The 3-alkyl-N-aryl-sulfonyl-4-amino-6-nitroanilines used as intermediates are obtained by dissolving in pyridine solution at 30 to 60 ° C and in a molar ratio of about 1 or equal to 1 benzenesulfochloride or p-toluenesulfochloride react with the 2-alkyl-5-nitro-p-phenylenediamines. The reaction is selective under these conditions and only the meta-amine function with respect to the nitro group reacts.

The reaction with the haloalkanes of the formula XRj or the alkyl sulfates such as methyl or ethyl sulfate can take place in alkaline aqueous medium between 40 and 60 ° C, in dimethylformamide in the presence of alkali or alkaline earth hydroxides, for example in the presence of lime. j

The hydrolysis of the substituted derivatives thus obtained can be carried out between 80 and 100 ° C with hydrochloric acid and preferably with concentrated sulfuric acid at about 0 C. j

In the particular case where Rj has the meaning j -CH "CH" OH, the preferred method consists of reacting chloroethyl chloroformate with 2-alkyl-5-nitro-p-phenylene-diamine followed by hydrolysis in water. alcohol solution of the; carbamate thus obtained with sodium or potassium hydroxide. j

The compositions of the invention are characterized in that in a cosmetically acceptable solvent medium they contain at least one compound of the formula I or a cosmetically acceptable salt thereof and they can be used for the direct dyeing of keratin fibers or for the oxidation dyeing of these fibers, in which case the compounds of the formula I or their salts (give complementary reflection to the base color obtained by oxidative development of the oxidation dye.) These compositions contain the compounds of the invention in amounts of 0.001 to 5 wt.% and preferably from 0.01 to 3% by weight, based on the total weight of the paint composition.

They can contain anionic, cationic, nonionic or amphoteric surfactants or mixtures thereof. These surfactants are present in the compositions of the invention in amounts from 0.5 to 55 wt.%, Preferably from 4 to 40 wt.%, Based on the total formulation. The cosmetic carrier is generally formed by water, but organic solvents may also be added to the compositions to dissolve the compounds which would not be sufficiently soluble in water. Such solvents are, for example, lower alkanols such as ethanol and isopropanol, polyols such as glycerol, glycols or glycol ethers such as 2-bu; oxyethanol, ethylene glycol, monoethyl ether of ethylene glycol, propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as analogous products and mixtures thereof. These solvents are preferably present in amounts of from 1 to 75% by weight and in particular from 5 to 50% by weight, based on the weight of the total preparation.

The preparations may be thickened, preferably with compounds such as sodium alginate. Gum arabic, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose and the various thickening polymers, such as, in particular, acrylic acid derivatives. It is also possible to use inorganic ester thickeners, such as bentonite. These thickeners are preferably present in amounts from 0.5 to 10 wt.% And especially from 0.5 to 3 wt.%, Based on the total weight of the preparation. j

The compositions of the invention may also contain various additives customary in hair dye compositions, especially penetrants, sequestrants, film-forming agents, tampons and perfumes.

The formulations can be in various forms such as liquids, creams, gels or any other form. getting a hair dye is appropriate. They may also be filled in aerosol bottles in the presence of a propellant. I

The pH of these paint preparations can be between 3 and 11.5, preferably between 5 and 11.5. The desired value is set with the aid of an alkalizing agent such as ammonia, sodium, potassium or ammonium carbonate, sodium or potassium hydroxide, an alkanolamine such as mono-, di- or triethanolamine, an alkyl amine such as ethylamine or triethylamine or with an acidifying agent such as phosphoric, hydrochloric, tartaric, acetic, lactic or citric acid. j

When the compositions are to be used for direct dyeing of hair, they may contain, in addition to the compounds of the invention, other direct dyes, such as azo or anthraquinone dyes, eg tetraaminoanthraquinone, benzene series nitro dyes other than the compounds of the formula 1 and in particular the following compounds: i 2-methyl-6-nitraniline, 3-nitro-A-aminophenol, i 3-nitro N-hydroxyethyl 4-aminophenol, 3-nitro-4-amino-6-methylphenol , 3-amino-4-nitrophenol, 2-amino-3-nitrophenol, 3-nitro-N - ^ - hydroxyethyl-6-aminoanisole, Ny ^, J ^ -dihydroxypropyl-3-amino-4-nitroanisole, ÖHnethyl-3 -amino-4-nitro) phenoxyethanol, (N-methyl-3-amino-4-nitro) phenyl, ^ dihydroxypropyl ether »N> N» (^ - hydroxyethyl) nitro-p-phenylenediamine and 3-ni tr oN '-me thy 1-4 -amino-N, N- (d i - ^ - hy dr oxye thy 1) ani 1 ine,

The paint compositions of the invention may also contain (3-nitro-N - $ hydroxyethyl-4-amino) phenoxyethanol and (3-nitro-N - hydroxyethyl-4-amino) phenyl dihydroxypropyl ether contain »that j are new connections. The present invention also relates to these two new compounds, the preparation of which is explained below.

The concentrations of these direct dyes other than the dyes of formula I may be between 0.001 and 5% by weight, based on the total weight of the composition. These compositions are applied to the keratinous fibers; for a residence time of 5 to 40 minutes and then the fibers are rinsed, optionally washed, rinsed again and dried.

The compositions can also be used as a capillary lotion for the water waves, which at the same time slightly colors the hair and strengthens the wave. In this case, the preparations are in the form of solutions in water, alcohol or alcohol and. water and contain at least a cosmetic resin and are added; applied to damp hair, which has been pre-washed and rinsed and, if necessary, curled and then dried »

The cosmetic resins used in the water wave lotions may include, in particular, polyvinyl pyrrolidone, crotonic acid vinyl acetate, vinyl pyrrolidone vinyl acetate, maleic anhydride nutyl phenyl ether or maleic anhydride methyl phenyl ether copolymers, any anionic non-cationic acids. ionic or amphoteric polymer, which is usually included in this type of composition. These cosmetic resins are present in the compositions of the invention in an amount of 1 to 3% by weight and preferably from 1 to 2 wt.%, based on the total weight of the preparation.

When the preparations are oxidation paints; use the compounds of the formula I of the invention in principle to confer the final color; The preparations then contain, in combination with at least one nitro dye of the formula 1, precursors of oxidation dyes. !

For example, they may contain p-phenylenediamines such as p-phenylenediamine, p-toluenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-dimethyl-3-methoxy-p-phenylenediamine, N- (y ^ -methoxyethyl) -p-phenylenediamine, N, N-di (? -hydroxyethyl) 4-aminoanili-; ne, N, N- (ethyl, carbamylmethyl) 4-aminoaniline and their salts .;

They may also contain p-arainophenols, for example p-arainophenol, N-methyl-p-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2-methyl-4-aminophenol, and their salts, j

They can also contain heterocyclic derivatives; for example 2,5-diaminopyridine and 7-aminobenzmorpholine. j

The compositions of the invention may contain couplers known in the art in combination with the oxidation dyes. j

Examples of these couplers are in particular m-diphenols such as resorcine, 2-methylresorcine, m-aminophenols such as mr aminophenol, 2-methyl-5-aminophenyl, 2-methyl-N - <- - hydroxyethyl) -5-aminophenol, 6- hydroxybenzorpholine and their salts, m-phenylene diamines such as (2,4-diamino) phenoxyethanol, 6-aminobenzmorpholine, / N - ^ - hydroxyethyl) 2-amino-4-amino-7-phenoxyethanol, (2,4-diamino) -phenyl-y4 [-dihydroxypropyl ether and their salts, m-acylamino phenols, m-taureidophenols and m-carbaroxy aminophenols such as 2-methyl-5-ace-tylaminophenol, 2-methyl-5-urea-phenophenol and 2-methyl-5-carbetoxy-aminophenol.

Finally, other couplers which can be included in the compositions of the invention include naphthol, couplers with an active methylene group such as diketo compounds and pyrazonones, and heterocyclic couplers such as 2,4-diaminipyridine, as well as their salts.

In addition to precursors of oxidation dyes, the compositions contain reducing agents, especially sodium sulfite, thioglycolic acid, thio lactic acid, sodium bisulfite, ascorbic acid and hydroquinone. These reducing agents are preferably present in amounts of from 0.05 to 1.5% by weight, based on the total weight of the composition. The precursors of oxidation dyes can be used in the compositions of the invention; in concentrations from 0.001 to 5% by weight and preferably from 0.03%! up to 2% by weight, based on the total weight of the composition. The couplers may also be present in amounts from 0.001 to 5% by weight, preferably from 0.015 to 2% by weight. Their pH is preferably between 7 and 11.5 and is adjusted with the above-defined alkalizing agents;

It has been found that the compounds of the invention are particularly stable in such compositions,

The method of dyeing keratinous fibers, especially human hair, which is developed by an oxidizing agent, consists of applying to the hair the dyeing composition, which simultaneously contains a dye according to the invention and dye precursors and developing the color with i an oxidizing agent, which is present in the dyeing composition, or is applied to the hair in a second treatment. :

Hydrogen peroxide, urea peroxide or persalts are preferably used as the oxidizing agent. In particular, a hydrogen peroxide solution of 20 volumes is used. Once the preparation has been applied to the keratin fibers with the oxidizing agent, it is left to stand for 10 to 50 minutes, preferably 15 to 30 minutes, after which the keratin fibers are rinsed, optionally washed with shampoo and again rinses and dries.

The following examples illustrate the invention

Preparation example 1

Preparation of 2-methyl-4-amino-5-nitro-N-4-hydroxyethylaniline.

The preparation proceeds according to the accompanying reaction scheme.

First stage

Preparation of 1-chloroethyl N- / (2-methyl-4-amino-5-nitro) phenyl-7-carbamate.

0.6 mol or 100 g of 2-methyl-4-amino-5-nitroaniline and 0.36 mol or 50 g of potassium carbonate are added in 500 ml of dioxane, to which 145 ml of water have been added. The mixture is brought to 90 [deg.] C. with stirring and then 0.6 moles or 86 g of chloroethyl chloroformate are added in small amounts in 10 minutes. When everything has been added, heating is continued for another 10 minutes at 90 ° C, the reaction mixture is cooled to 15 ° C and the desired product is then filtered off. After washing with a little dioxane and then with water and alcohol, the product is recrystallized from dioxane and then dried under vacuum. It melts at 192 ° C.

!

Second stage |

Preparation of 2-methyl-4-amino-5-nitro-N- / g-hydroxyethylaniline.

In 2625 ml of water-alcohol solution (30Z H 2 O, 70Z ethanol) containing 9.32 mol or 522 g of potassium hydroxide, 1.86 mol or 510 g of -chloroethyl-N- is added in 15 min with stirring at 55 ° C. / "(2-methyl-4-amino-5-nitro) phenylcarbamate. The temperature rises to 72 ° C. When everything is added, a liter of water is added more to the reaction medium, while the temperature is kept between -70 and 75 ° C. The reaction medium is filtered hot to remove a slightly insoluble matter. 5L of ice water is added to the filtrate, then neutralized with acetic acid. The desired product precipitates. It is filtered, washed with water and recrystallized from alcohol. After drying under vacuum, it melts at 141 ° C.

Preparation example 2

Preparation of 2-methyl-4-amino-5-nitro-N- / diethylaminoethylaniline,

The preparation proceeds according to the accompanying reaction · "scheme B.

First stage

Preparation of 3-methyl-N-tosyl-4-amino-6-nitraniline.

0.149 mol or 25 g of 2-methyl-5-nitro-p- is dissolved phenylenediamine in 75 ml of pyridine. To this pyridine solution, 0.161 mol or: 30 g of p-toluenesulfochloride is added in small bits at 40 ° C with stirring, and the reaction medium is then kept at 40 ° C for another 4 hours. The pyridine solution is then poured into 600 g of ice water.

The desired product precipitates by adding hydrochloric acid. It is suctioned, washed with water and recrystallized; it then tallizes from acetic acid. After drying under vacuum, it melts at 174 ° C.

Second stage

Preparation of 3-methyl- (Ν, Ν-diethylaminoethyl, tosyl) 4-amino-6-nitraniline.

0.02 mol or 6.42 g of 3-methyl-N-tosyl-4- are added; amino-6-nitraniline and 0.03 mol or 1.68 g of lime in 24 ml of dimethylformamide. The mixture is brought to 80 ° C and then added in clay; Add little bits with stirring to 0.022 mol or 3.8 g of diethylaminoethyl chloride. The temperature is kept at 80 ° C for 1 hour and 15 minutes and then the reaction medium is poured into 100 ml of ice water. The desired product precipitates. It is sucked off, washed with water and re-! it then crystallizes from dioxane. After drying under vacuum at 50 ° C, it melts at 181 ° C.

Third stage

Preparation of 2-methyl-4-amino-5-nitro-N-diethylaminoethylaniline.

0.0426 is introduced in small bits with stirring

J

moles or 17.9 g of substituted p-toluenesulfonamide obtained in the previous step in 90 ml of 0 ° C sulfuric acid. When all is dissolved, the reaction medium is kept at 0 ° C for 3 hours and poured ! then out on 700 g of crushed ice. Neutralize with ammonia. The desired product, which has been precipitated, is filtered off. After it is washed with water, dried and recrystallized from ethyl acetate, it melts at 78 ° C.

Preparation example 3

Preparation of 2-methyl-4-amino-5-nitro-N-methylaniline. !

The preparation proceeds according to the accompanying reaction scheme C.

First stage

Preparation of 3-methyl-N, N-methyl-4-tosylamino-6-nitraniline.

0.05 mol or 16.05 g of 3-methyl-N-tosyl-4- | is dissolved amino-6-nitraniline, obtained according to the first step of the preparation example 2, in 110 ml of 0.5N sodium hydroxide at 40 ° C.

To this sodium hydroxide solution, 0.055 mol or 6.93 g of dimethyl sulfate is added dropwise with stirring, while the pH is adjusted. keeps calm. After 2 hours at 40 ° C, the reaction medium is cooled and the desired product is filtered off. It is washed with cold 0.5N sodium hydroxide solution and then with water. After two recrystallizations from acetic acid and drying under vacuum, it melts at 160 C. j

Second stage

Preparation of 2-methyl-4-amino-5-nitro-N-methylaniline.

0.239 ml of ULO g, obtained in the first stage, is substituted in small bits with stirring, substituted p-! toluene sulfonamide in 40 ml of 0 ° C concentrated sulfuric acid. i

The dissolution takes place slowly. When everything is dissolved, the reaction medium is kept at 0 ° C for 2 hours and then poured onto 400 g of crushed ice. The desired product precipitates: in sulphate form. The sulfate is filtered off and then redissolved in water. The 2-methyl-4-amino-5-nitro-N-methylaniline is precipitated by adding ammonia. The product is filtered off with suction, washed with water and dried under vacuum. After recrystallization from benzene, it melts at 136 ° C,

Preparation example 4

Preparation of 2-methyl-4-amino-5-nitro-N-dihydroxypropylaniline.

This compound has the formula 3.

0.2 mol or 33.4 g of 2-methyl-4-amino-5-nitraniline and 0.1 mol or 10 g of calcium carbonate, suspended in 100 ml of water, are preheated on a boiling water bath with stirring. 0.216 mol or 24 g of 1-chloropropanediol-2,3 are added. The reaction mixture is heated on boiling water bath for 24 hours while adding 0.035 mol or 3.5 g of calcium carbonate and 0.066 mol or 7.3 g of 1-chloropropanediol-2,3 at the same time seven times, each time after 3 hours. The reaction mixture is filtered warm and the filtrate is diluted with 60 ml water. After cooling at 0 ° C for 24 hours, the desired product, which has crystallized out, is filtered off. The product is washed with water and recrystallized three times from ethanol. It melts at 150 ° C.

Preparation example 5

Preparation of 2-methyl-2-amino-5-nitro-N-β-aminoethylaniline. j

This compound has the formula 4.

A suspension of 0.05 mol or 8.35 g of 2-methyl-4-amino-5 "n-traniline and 0.035 mol or 3.5 g of calcium carbonate in 100 ml of water is preheated on a boiling water bath with stirring. ; ΐ

0.07 mol or 14.35 g of bromoethylaniline hydrobromide in solution in 20 ml of water are added in small amounts while stirring. After heating for 2 hours on boiling water bath, the reaction medium is filtered warm. After cooling the filtrate at 0 ° C for 24 hours, the desired product, which has crystallized out in the form of the hydrobromide, is filtered off. The crude product is washed with acetone and then recrystallized from boiling water. After suction, washing with acetone and drying in vacuo, the hydrobromide monohydrate of 2-methyl-4-amino-5-nitro-N-amino-aminoaniline is obtained. *

! j i i i! i

The hydrobromide thus obtained is dissolved in water. After alkalinization with 2N sodium hydroxide, the 2-methyl-4-amino-5-nitro-N-aminoethylaniline is filtered off. After washing with water, drying and recrystallizing from ethyl acetate, the product melts at 105 ° C.

Preparation example 6

Preparation of 2-methyl-4-amino-5-nitro-N-propylaniline.

This preparation proceeds according to the accompanying reaction schedule D.

First stage

Preparation of 3-methyl-N, N- (propyl, tosyl) -4-amino-6-nitraniline.

0.164 mol or 52.5 g of 3-methyl-N-tosyl-4-amino-6-nitraniline obtained in the first step of preparation are dissolved; Test Example 2 in 210 ml of dimethylformamide. 0.090 mole or 5.04 g of quicklime is added. The mixture is brought up to Spring at 60 ° C and then add 0.18 mol, or 16.4 µl propyl bromide, in small amounts with stirring. After 2 hours at 65 ° C, 0.019 mol or 1.08 g of quicklime and 0.036 mol or 3.28 µl of propyl bromide are added simultaneously with stirring. Heating is continued for 2 hours. The reaction medium is filtered warm and the filtrate is then diluted with 2 l of ice water. The desired product precipitates. It is aspirated and washed twice with 1N sodium hydroxide solution and then with water. After recrystallization from acetic acid and drying under vacuum, it melts at 170 ° C.

Second stage

Preparation of 2-methyl-4-amino-5-nitro-N-propylaniline.

______________________________i

Substituted p-toluenesulfonamide in 235 ml of 0 ° C concentrated sulfuric acid is obtained in small bites, while stirring, 0.129 mol or 47 g of the first stage obtained p-toluenesulfonamide.

When everything is dissolved, the reaction mixture is left to stand for 6 hours; spring at 0 ° C and then pour it onto 2.3 kg of crushed ice. The desired product precipitates in sulfate form. The sulfate is filtered off and washed with a little cold water. The suspension is suspended. in 50 ml of water and then pour this suspension into 50 ml of pyridine with stirring. Stirring is continued for an additional 30 minutes and then 500 ml of water are added. The 2-methyl-4-amino-5-y-nitro-N-propylaniline is filtered off, which melts at 115 DEG C. after washing with water, drying and re-seeding from toluene.

Preparation example 7

Preparation of 2-methyl-4-amino-5-nitro-N-ethylaniline.

This preparation proceeds according to the accompanying reaction scheme E.

First stage • Preparation of 3-methyl-N.N- (ethyl, tosyl) -4 "amino-6-nitraniline.

0.04 mol or 12.84 g of 3-methyl-N-tosyl "4", amino-6-nitraniline, obtained according to the first step of Example 2, are dissolved in 50 ml of dimethylformamide. 0.024 mol or 1.34 g of quicklime is added. The mixture is brought to about 50 ° C and then 0.048 mol or 6.47 ml of ethyl sulfate are added in small amounts with stirring. The reaction medium is kept at 50 ° C for 6 hours and then filtered hot. The cooled filtrate is added to 500 g of ice water. The desired product precipitates in crystal form. It is filtered off and washed twice with 1N sodium hydroxide solution and then with water. After recrystallization from acetic acid and drying under vacuum, it melts at 184 ° C.

.Second stairs

Preparation of 2-methyl4-amino-5-nitro-N-ethylaniline.

0.0715: mol or 25 g of the substituted p-1 obtained in the first step is introduced in small bits with stirring. toluene sulfonamide in 125 ml of 0 ° C sulfuric acid. When everything is dissolved, the reaction medium is kept at 0 ° C for 6 hours and then poured onto 1,250 kg of crushed ice. The desired product precipitates in sulfate form. The sulfate is filtered off and then washed with a little cold water. It is then suspended in 50 ml of water and this suspension is poured into 50 ml of pyridine with stirring.

Namin. stirring, 500 ml of water are added. The 2-ym methyl-4-amino-5-nitro-N-ethylaniline is filtered off, which after washing with water, recrystallization from a dimethyl sulfoxide / water mixture 50/50 and drying under vacuum at 125 ° C,

i i __1

Preparation example 8

Preparation of 2-isopropyl-4-ammo-5-nrtro-N-methylaniline »

This preparation proceeds according to the attached reaction scheme F.

First stage

Preparation of 3-Isopropyl-N-tosyl-4-amino-6-nitraniline.

Hen dissolves 0.0947 mol or 18.5 g of 2-isopropyl-4-amino-5-nitraniline (melting point 68 ° C) in 47 ml of pyridine. 0.1 mol or 19 g of p-toluenesulfochlo- is added in small amounts with stirring. Ride in such a way that 50 ° C is not exceeded. When all is added, the reaction medium is kept at 50 DEG C. for another 30 minutes and then poured onto 350 g of crushed ice. The desired product precipitates in the form of yellow crystals. It is filtered, washed with water, dried and recrystallized from ethanol. After drying under vacuum, it melts at 178 C.

Second stage

Preparation of 3-siopropyl-N, N- (methyl, tosyl) -4-amino-6-nitrani-; line.

0.061 mol or 21 g of 3-isopropyl-N-tosyl-4- is dissolved; amino-6-nitraniline in 60 ml of dimethylformamide. 0.072 mol or 4 g of lime is added. 0.072 mol or 9.1 g of methyl sulphate is introduced into the reaction mixture in small amounts with stirring, while the temperature is maintained between 40 and 45 ° C. When all is added, the mixture is allowed to stand at 45 ° C for an hour, then it is filtered and poured into 350 ml of ice water. The desired product is precipitated in the form of yellow crystals. It is filtered off with suction, washed with water and recrystallized from ethanol. After drying, it melts at 15A ° C.

Third stage

Preparation of 2-Isopropyl-4-amino-5-nitro-N-methylaniline.

Substituted p-j toluene sulfonamide obtained in 60 ml of 96Z is added in small bits with stirring, 0.052 µmol or 18.9 g of the second stage, while keeping the temperature between 15 and 20 ° C. When everything is resolved, let j. 1 reaction medium at 2 ° C for 2 hours and then pour on 600 g:! crushed ice. The desired product precipitates in sulfate form. j

O I

It is filtered off and then placed in 100 ml of water at 40 C. j

It is then made alkaline with stirring using 20% ammonia. The 2-isopropyl-4-amino-5-nitro-N-methylaniline is extracted. The product is washed with water, dried and recrystallized from cyclohexane.

After drying, it melts at 105 ° C.

Preparation example 9

Preparation of 2-ethyl-4-amino-5-nitro-N-methylaniline.

This preparation proceeds according to the accompanying reaction scheme 6.

First stage

Preparation of 3-ethyl-N-tosyl-4-amino-6-nitraniline.

0.087 mol or 15.8 g of 2-ethyl-4-amino-5-nitraniline (melting point 138 ° C) is dissolved in 45 ml of pyridine. 0.092 mol or 17.5 g of p-toluenesulfon chloride is added in small amounts with stirring such that 50 ° C is not exceeded. When all is added, the reaction medium is kept at about 50 ° C for 30 min and then poured onto 350 g of crushed ice. The desired product precipitates in crystal form. After suction, washing with water, drying and recrystallization from alcohol, it melts at 182 ° C.

Second stage |

Preparation of 3-ethyl-N, N-methyl, tosyl-4-amino-6-nitraniline.

0.061 mol or 20.1 g of 3-ethyl-N-tosyl-4-amino-6-nitraniline is dissolved in 60 ml of dimethylformane. 0.072 mol or 4 g of lime is added. The reaction mixture is brought to about 40 ° C and then 0.072 mol or 9.1 g of methyl sulfate is added in small amounts with stirring. When all is added, the reaction medium is kept at 45 ° C for 1 hour. It is filtered and then poured. filtrate on 350 g of crushed ice. The desired product precipitates in crystal form. It is filtered off with suction, washed with water and recrystallized from alcohol. After drying, it melts at 167 ° C.

Third stage

Preparation of 2-ethyl-4-amino-5-nitro-N-methylaniline.

0.0466: mol or 16.3 g of the second stage substituted p-toluenesulfonamide obtained in 55 ml of sulfuric acid of 96Z are added in small bits, with stirring, while maintaining the temperature between 15 and 20 ° C. When everything is resolved, one keeps. the reaction medium at room temperature for another 2 hours and then pour it; 500 g crushed ice. The desired product precipitates in; sulfate form. It is sucked off and then it is taken up again in 200! ml water at 40 ° C and alkaline with 20 Z ammonia while stirring. The 2-ethyl-4-amino-5-nitro-N-methylaniline is filtered off in the form of red crystals. After washing with water, drying and recrystallization from benzene, the product melts at 123 ° C.

Preparation example 10

Preparation of 3-nitro-4-amino-6-methyl-N - (/ - hydroxypropyl) aniline. _____ This ^ compound has ^ the formula 5 _ ^ ___! ------ j

It is heated on boiling water bath with stirring 16.7 µg or 0.1 mol 3-nitro-4-amino-6-methylaniline, 40 ml water, 6.6 g or 0.066 mol calcium carbonate and 12.42 g or 0.132 mol 3- chloropropol-1 for 7 hours and 30 million

After filtration in the heat, the filtrate is cooled with an ice bath. The desired product crystallizes out. 5.15 g of 3-nitro-4-amino-6-methyl-N- (1H-hydroxypropyl) aniline are recovered by birch crystallization from ethanol at 96 [deg.] and chromatography on an eilica column. Melting point: 150 C.

Elemental analysis calculated for ciAA ° j I.

Theory Found CZ 53.33 53.25 HZ 6.67 6.59 NZ 18.67 18.75 OZ 21.33 21.20

Preparation example 11

Preparation of 3-nitro-4-amino-6-methyl-N- (paminopropyl) aniline. This compound has the formula 33 g or 0.2 mol 3-nitro-4-amino-6-methylaniline and 20 g or 0.2 mol calcium carbonate, suspended in 1 ml of water and heated in boiling water bath. 87.8 g or 0.4 mol of bromopropylamine hydrobromide dissolved in 85 ml of water are then poured into this mixture in 15 min.

The reaction medium is then kept under stirring; 5 hours and 30 minutes on boiling water bath. j

After filtration in the heat, the filtrate is removed. cooled with an ice bath. The desired product crystallizes out in hydrobromide form.

The hydrobromide is dissolved in 500 ml of water and released in concentrated sodium hydroxide.

Recrystallization from 96 ° alcohol gives 13.3 g of 3-nitro-4-amino-6-methyl-N - (- aminopropyl) aniline, which melts at 164 ° C.

Elemental analysis calculated for cj qH16N4 ° 2

Theory Found CZ 53.57 53.61 HZ 7.14 7.15 NZ 25.00 25.09 OZ 14.28 14.55

Example I

Them prepares the following paint preparation: 2-Me thy 1-4-amino-5-ni tro-N-jJ-d ie thy 1 aminoethy1-aniline .................. ................................. 0.25 g-

Propylene glycol ................................. 5 g 2-Butoxyethanol ........... ............................... 5 g

Carboxymethyl cellulose ...... 10 g, i

Honoethanolamine ......................................... 5 g ';

Water as needed until ....................... 100 g1 PH 9.5 o

When this mixture is applied at 30 ° C for 25 minutes on white-bleached hair, it imparts a bright red color to this hair after rinsing and shampooing.

Example II

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-hydroxyethylaniline ......... 0.3 g of 2-Butoxy ethanol ......... ................................. 10 g '

Alfol C, 6 / C18 ............................................ 8 g

Used to be................................................. ..... 0.5 g

Cemulsol B ............................................... 1 g

Oil acid diethanolamide. 1.5 g

Triethanolamine .......................................... 1 g

Water as needed until ...................................... 100 g pH 9!

When this mixture is applied to white-bleached hair for 30 minutes at 30 ° C, it imparts a bright red color to this hair after rinsing and shampooing. j

____ I

Example III

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-hydroxyethylaniline, ... 0.25 g, 2-Amino-3-nitrophenol .. 0.21 g .

3- Nitro-N-hydroxyethyl-6-aminoanisole ................. 0.08 g '

Tetraamineant rachinone ..... 0.055 g; 2-Butoxyethanol ..............,. 6 g |

Propylene glycol ..................................., ...... 4 g |

Carboxyraethyl cellulose ................................... 1 ° g!

Monoethanol amine ......................................... 6 g! j

Water as needed until ...................................... 100 g pH 10.5

When this mixture is applied to 90% white hair for 20 min at 30 ° C, after rinsing and shampooing, it imparts a bright chestnut color with copper sheen.

Example IV

The following paint preparation is prepared; 2-Methyl-4-amino-5-nitro-N - - - hydroxyethylaniline 0.3 g 2-Amino-3-nitrophenol ..., .... ,,. ,, .......... .,. 0 ... 0 ... 4.0. 0.4 g j -

Tetraaminoanthraquinone .................................... 0.2 g! 2-Butoxyethanol .......................................... 6 g! i

Lunic acid monoethanolamide. «..« «, ..., .. 9.,. ,, 0.490, .00 ,, 1.5 g, i

Lauric acid .............................................. 1 g I

i

Hydroxyethyl cellulose ,,, .. 5 g '

Monoethanolamine 2 g

Water as needed until ...................................... 100 g ^ pH 10 j

When this mixture is applied at 28 ° C for 30 min on natural 90% white hair, after rinsing and shampooing, it imparts a medium chestnut color with red copper sheen.

Example V

The following paint preparation is prepared; ; 2-Methyl-4-amino-5-nitro-N-diethylaminoethylaniline ,,, 39 g

3- Nitro-4-araino-6-methylphenol ............................ g I

3-Nitro-N'-methyl-4-amino-N, N- (di-1-hydroxyethyl) -aniline, 0.4 g 2-Butoxyethanol ........... v.,. .............. 10 g

Carbopol 934 ..................................... 2 g

Ammonia 22 ° D ............................................ 5 g

Water as needed until yoo g! pH 10

When this mixture is applied to decolorized hair for 25 minutes at 28 ° C, it gives this hair a very red chestnut color after rinsing and shampooing.

Example VI

The following dyeing preparation was prepared: 2-Methyl-4-amino-5-nitro-N-hydroxy-ethylaniline, ..... 0.2 g of 3-Nitro-N-hydroxyethyl-4-aminophenol. 0.15 g (N-methyl-3-amino-4-nitro) -enyl, dihydroxypropyl ether. ] g

Tetraamine anthraquinone ......... 0.25 g I

2-Butoxyethanol .......................................... 5

Propylene glycol .......................................... 3

O

Cemulsol NP ^ J2 g

Cemulsol NPQ ..... 15 y o j

Oil alcohol, oxygenated with 2 moles of ethylene oxide .. 5 g: Oil alcohol, oxygenated with 4 moles of ethylene oxide, 5 ^ 5 g

Water as needed until ...................................... 100 µl pH 7.2.

When applied to 95% white, permed hair for 30 minutes at 28 ° C, this mixture imparts a deep blond color with golden glow to this hair after rinsing and shampooing. '

Example VII

The following paint preparation is prepared: 2- Methyl-4-amino-5-nitro-N-hydroxyethylaniline ......... 0.155 g 3-Nitro-4-aminophenol .......... 0.5 g N, N '- (hydroxyethyl) nitro-p-phenylenediamine ... 0.05 g; 3-Nitro-N'-methyl-4-amino-N, N- (di-hydroxyethyl) aniline., 0.2 g 2-Butoxyethanol ................. .................. o. · «··. · 10 g

Coconut fatty acid diethanol amides 2.2 g

Lauric acid .............................................. 0.8 g

Monoethyl ether of ethylene glycol ........................ 2 g

Monoethanolamine * ..... ... o ..... 1.05 g

Water as needed until ................................. 100 g pH 8.8.

When this mixture is applied to natural 90% white hair for 20 minutes at 30 ° C, it imparts a deep red copper color to this hair after rinsing and shampooing.

Example VIII

The following paint preparation is prepared! • 2-Methyl-4-amino-5-ni.tro-N - ^ - hydroxyethylanj.line ..... o ... 0.22 g

Resorcine .............. 9.0 ............. 000000 .... 00..9 ... 0.055g in-aminophenol ... ...o ........ 0.15 g ^ p-Phenylenediamine ,,,, .....................,. 0 ... .0.0, .... 0.05 gjp — Aminophenol ................. «o ... 0.0..0 ,. 0.2 g of 2-Methyl-N - - - hydroxyethyl-5-aminophenol ,,, .... 90..0.0 .... 0 0.05 g of Cemulsol NP ^ ,,,,,,,., , .... ,, .., ........ 00000,00000,., .... 12 g 1

Cemulsol NP ^ ............................................. 15 g ;

Oil alcohol with 2 moles of ethylene oxide,,,,,,,..., 0 ... 1 | 5 g; Oil alcohol with 4 moles of ethylene oxide, .0.0, .0.0, .00., 1.5 g

Propylene Glycol ..., 0, .0..000000, .00, .0 6 8:

Trilon B ,, 00, .00 .., 0.00 .., 0.12 g i

Ammonia 22 ^ B, ·, ·· «, ·..,., <..». * »<«., »0,0,00000., 00.0.0» ». 11 8 1

Thioglycolic acid. ,,,,,,,,., ........, ... 00000000, 00.0, .0, .0 0.6 g

Water as a need to ,,,, ..., ...,. ,, ... 0., 00.00000, 0.000.0 100 g; pH 10.5.

At the time of use, 100 g of hydrogen peroxide 20 volumes are added. j

When this mixture is applied to straw-colored hair for 30 min at 30 ° C, after rinsing and shampooing, it imparts a medium chestnut color with copper sheen to this hair.

Example IX

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-methylaniline ............. 0.2 g

2-Butoxyethanol .......................................... 10 g I

Carboxymethyl cellulose ........................... ·······. 2 g

Ammonium lauryl sulfate ..................... 5 g

Ammonia 22 ° B ......................... 0.5 g

Water as needed until ...................................... 100 g pH 9.5.

When this mixture is applied to hair that has been bleached for 25 minutes at 30 ° C, it imparts this hair after rinsing: and shampooing has a slightly pupating red color.

Example X.

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-methylaniline ................. 0.5 g of 2-Methylresorcine ..... ·····. ····· .. * .. ·. * ... ·. ·. ·· ...... 0.15 gj m-Aminophenol ......... .................................... 0.05 c 'p-Ammo phenol ....... ...................................... 0.4 g! p-Phenylenediamine ........................................ 0.08 µg 2-Methyl -N - ^ - hydroxyethyl-5-aminophenol ... 0.15 g

Cemulsol NP ^ .................. 21 gi 9

Oil acid ................................................ .4 g of 2-Butoxyethanol ..................... ..................... 3 g

Ethanol 96 ° .............................................. 10 gj

Masquol DTPA ............................................ 2.5 gi

Thiogly col acid .......................................... 0.6 g:

Ammonia 22 ° ............................................. 10 gj

Water as needed until ..................................... 100 gi pH 10.3. | i

At the time of use, 100 g of water!

dust peroxide 20 volumes. I

____________i

When this mixture is applied at 30 ° C for 30 min.

. / I

applied to natural, 90Z white hair, after rinsing and shampooing it imparts a bright chestnut color with red copper sheen.

When a paint preparation is applied to hair of the same origin under the same conditions, which differs from the previous preparation only in the absence of: 2-methyl-4-amino-5-nitro-N-methylaniline, a fairly dull beige shade is obtained.

Example XI

They prepare the following paint composition: Dihydrochloride of N ^ -methoxyethylamino-4-aminobenzene 1 gp — Ammophenol m ·· ·. · M <· <· ·> m ·· n η i> · «·> <> κβ · <t 0.3 gi

Resorcine. »...... o o ......... 0a25 g j m-Aminophenol 0.25 g; 2-Methyl ”4-amino-5-nitro-N-hydroxyethyl aniline ....... 0.4 g

Oil alcohol, glycerated with 2 moles of glycerol .......... 5 g

Oil alcohol, glycerated with 4 moles of glycerol 5 g

Oleic acid .......... · «...« · .. · <««. «. ·» »···» β ···· »· ββ ···· 3 g

Oil acid diethanolamine, γ ..... · ............ ο ... ·. 5 g

Oil acid diethanolamide, .................... 90 ...... 0..0 12 g;

Ethyl alcohol ........................................... 10 g,

Ethyl glycol ............................................ 12 g j

Ethylenediametetraacetic acid .. ¢ ,, ....... 99. .O". . · «.. ·· 0.2 g

Ammonia 22 ^ B,. ,, ... 0 ... 909.9.9 ........ 9.09.9.0..00 ... 0 10.2 g:

Sodium bisulfite 35 ° B ................................. 1.3 g I

Hydroquinone ..., ...,. 9 ........... 9.9.9..00.000.0.00 ... 0. 0 s 15 g.

1-phenyl "3-methyl-5-pyrazolone. 9, ... 9 .... 00.0 ... 000 ... 0 0.15 g [

Water as needed until .......,.,.,., ....... 0 ... 0 .... 000..0 100 „g.

At the time of use, this liquid paint preparation is diluted with an equal amount of hydrogen peroxide 20 volumes.

The resulting gel is applied for 30 minutes. brought on a bright chestnut haircut. j

After rinsing, shampooing and drying, the hair is colored in a blonde shade with mahogany pearlescent sheen. {The color result obtained is almost identical, when using a freshly prepared liquid paint preparation or! with a preparation which has been stored for a long time after preparation.

Example XII

The following dyeing preparation is prepared: 2-Methyl-4-amino-5-nitro-N -, -, - - dihydroxypropylaniline,, 0.5 g

Fropylene glycol ........... 10 g:

Lauric acid monoethanolamide 1.5 g!

Lauric acid .................................. 1 g!

Hydroxyethylcellulose ,,,,,,,,, ........................... 5 g!

Monoethanolamine ......................................... 2 g

Water as needed until ...................................... 100 g 1 pH 10.

When this mixture is applied for 20 min. At 30 ° C to hair which has been bleached white, after rinsing and shampooing, it imparts a red color of 1.25 R 4/8 according to the Munsell value ring.

Example XIII

The following paint preparation is prepared: Hydrobromide monohydrate of 2-methyl-4-amino-5-nitro-Ny $ -aminoethylaniline .......................... ............ 0.81 g of 2-Butoxyethanol ............................... ........... 10 g 'ί

Coconut fatty acid diethanol amides .............................. 2.2 g

Lauric acid .............................................. 0.8 g:

Monoethyl ether of ethylene glycol ............. 2 g1 202 Monoethanolamine solution ...... · * ........... · ... · .. ·· 3 - gj

Water as needed until ...................................... 100 g ï pH 10.! • i

When this mixture is applied to 902 white natural hair at 28 ° C for 30 min, after rinsing and shampooing, it imparts a red color of 3.75 R 3.5 / 5 according to Munsell; appreciation,

Example XIV

The following paint preparation is prepared: 2- Methyl-4-amino-5-nitro-N-propy 1 ani 1 ine ............... 0.22 g

Dihydrochloride of 3-nitro-N, - - aminoethyl-4-amino-N 'N' - di - ^ - hydroxyethylaniline .... ,, .................. .......... 0J6 g 3- Nitro-4-aminophenol ................ 0 4 g! 2-Ethoxyethanol ......................... 10 g

Lauric acid monoethanolamide ............. ic „.............,. ,,., 4 ,,,,. ,,,,, 1,3 g

Lauric acid ................ i

Hydroxyethyl cellulose ..................................... 5 g

Monoethanolamine ...... ····· «·« ............................ 2 g

Water as needed until ........................ ,, ............. 100 g pH 10.

When this mixture is applied to 90% white natural hair for 25 minutes at 28 ° C, it rudishes this hair after rinsing and shampooing.

Example XV

The following paint preparation is prepared 2-Methyl-4-amino-5-nitro-N-propylaniline ............ 0.36 g; 2-Ethoxyethanol ............ 0 «!

CarboDol 934 _ '................................. 0., ... 0,, 4 ,, 2 gj 20% Monoethanolamine solution ..... jq g!

Hater as needed until ....................................... I00 g | pH 8.

When this mixture is applied for 25 min. At 30 ° C to hair that has been bleached, it gives it after rinsing! and shampoo a salmon red color.

Example XVI

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N, - - aminoethylaniline 0.02 g

Tetraaminoanthraquinone ................. 0.05 g 2-Methyl-4-amino-5-nitrophenol ................. ........... 0.05 g

Lauric acid monoethanolamide ... 1.5 g

Lauric acid ............, .., ..,. ,, .. ,,,. ,, 1 .... ,,,,,,,. ,, 1 g

Hydroxyethyl cellulose 5 g

Mono ethanol amine ........................................ 2 g

Water as needed until ...................................... 100 g pH 7.

When this mixture is applied at 30 ° C for 25 minutes on hair which has been bleached white, it imparts a sandy color with golden glow to this hair after rinsing and shampooing.

Example XVII

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-methyl-dihydroxypropylaniline, ... 0.05 g! (N-methyl-3-amino-4-nitro) phenyl, ^, ^ dihydroxypropyl ether, 4 0.05 µg N- ^ hydroxyethyl-2-amino (di - ^ - hydroxyethyl-4-aminoanilino) - 5-benzoquinone- 1.4 ....................................... 0.11 g

Carboxymethyl cellulose .................................. 2 g

Ammonium lauryl sulfate .................................. 5 g 4% Ammonia solution in water 0.5 g!

Water as needed until ..................................... 100 g "; pH 8.

When this mixture is applied at 30 ° C for 20 minutes; applied to hair bleached white, after rinsing and shampooing it imparts a blonde color with golden glow.

Example XVIII

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-y4-hydroxyethylaniline ........ 0.125 g 4-Nitro-N, N, -y4 "hydroxyethyl orthophenylenediamine ..... ... 0.165 g

Tetraaminoanthraquinone .................................. 0.26 g

Coconut fatty acid diethanol amides ............................. 2.2 g

Lauric acid ............................................. 0.8 g '

Monoethyl ether of ethylene glycol ....................... 2 g

Monoethanolamine ....... ···. *. ······. ·· «.. · .. · ... *». ···· 1 g

Water as needed until ...... ·. ······. ·. ··. ·. ···. ·. ··· * ···· 100 g pH 7.

When this mixture is applied at 28 ° C for 30 minutes; applied to decolorized hair, after rinsing and shampooing, it imparts a blonde color with mahogany.

When the above nitro dyes are replaced with the following dyes: 2-Methyl-4-amino-5-nitro-N - ^ - hydroxyethylaniline ........ 0.08 g! 2-Methyl-4-nitro-5-nitro-N-dihydroxypropylaniline ... 0.1 g A blond color with mahogany is obtained under the same conditions.

Example XIX

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N'y-aminoethyl-aniline ......... 0.01 µl 3-Nitro-N-hydroxyethyl -4 "amino / phenoxyethanol ........ 0.25 µg S-Nitro-N-methyl - ^ - amino-N *, N" "diy hydroxy-ethyl aniline .. 0.2 g! 2-Butoxyethanol ........................ 0..0.00 .......... 10 g

Cemulsol HP ^ ............................. o .............. 12 g

Cemulsol NP »............................ o ............... 15 g! * I

Oil alcohol, ethoxylated with 2 moles of ethylene oxide ... 1.5 g

Oil alcohol, ethoxylated with 4 moles of ethylene oxide ... »1.5 g '10% Lactic acid solution 0.5 g,

Water as needed up to 100 g j

pH 6.5. I

When this mixture is applied for 20 minutes at 28 ° C to hair that has turned white, it gives this hair after shampooing and shampooing a champagne rosé color.

Example XX

The following paint preparation is prepared: 2- Me thy 1-4-amino-5-nitro-Ny ^ -hydroxye thy1 aniline ,,,,,,,,, 0,11 µl 3-Nitro-N- -hydroxyethyl- 4-amino7phenyl, ^, ^ - dihydroxy-propyl ether ......................... 0.15 g 3-Nitro-N-methyl-4- amino-N ', Ν'-dihydroxyethylaniline, 0.15 g 2-Methyl-6-nitroaniline ............. 0.18 g 2-Butoxyethanol ..... .............. 10 g;

Alfol Cj / yg 8 g |

Used to be ................................................. .... 0.5 g |

Cemulsol B ...................] g

Oil acid diethanolamide ................................... 1.5 g '10Z Lactic acid solution ....... ............................. 0.5 g!

Water as needed until ...................................... 100 g pH 7.

When this mixture is applied at 25 ° C for 35 minutes; raised to straw-yellow discolored hair, it imparts this after i

rinse and shampoo a chestnut color with copper sheen. Example XXI

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-1-dihydroxypropylaniline ... 0.2 g N-hydroxyethyl-1-amino-S-nitrophenol ...... .........; .... 0.15 gi

Resorcine ................................................. 0.2 gj nr-Aminophenol ........................................... .0.15 g 1 p-Phenylenediamine ........................................ 0.15 g '| p-Aminophenol ............................................. 0, 15 gy

Remcopal 334 ..................... 21 g j

Remcopal 349 24 g 'i

Oleic acid ............... ··· ... · ». · ....................... 4 g! i 2-Butoxyethanol .......................................... 3 g!

Ethanol 96 ° .............................................. 10 gj

Masquol DTPA ............................................ 2.5 g :

Sodium bisulfite 35 ° B .................................... 1 g!

Ammonia 22 ° B ............................................ 10 g ;

Water as needed until ...................................... 100 g 1 pH 10.6.

At the time of use, 100 g of hydrogen peroxide 20 volumes are added.

When this mixture is applied to 90Z white natural hair at 28 ° C for 20 minutes, it imparts this hair after rinse | and shampoo a dark blond color with golden glow.

Example XXII

The following paint preparation is prepared: 2-Ethyl-4-amino-5-nitro-N-methylaniline ............ 0.45 g of 2-Butoxyethanol ....... ................ ............ 9 gy

Coconut fatty acid diethanol amides .............................. 2.2 g j

Lauric acid ............................................. 0.8 g j

Monoethyl ether of ethylene glycol ......... ............... 2 g

Monoethanolamine .. ,, «. ,,« «,,,,, ο009» ββο „·, 0 ,,, οβ, 00 # β 1 g

Water as needed until ...................................... 100 g pH 6.6.

When this mixture is applied for 25 minutes at 30 ° C to hair that has been bleached white, it imparts a bright red color to this hair after rinsing and shampooing.

Example XXIII

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-ethylaniline 0.33 µg 2-Butoxyethanol ...................... .................... 10 g |

Carboxymethyl cellulose .................................. 2 g! • ·

Ammonium lauryl sulfate .................................. 5 g 4% Ammonia solution .......... .......................... „0.2 g

Vflt & r as needed until ...................................... 100 g pH 7.

o o

When this mixture is applied for 30 min at 30 ° C to hair that has been bleached white, it gives this hair a bright red color after rinsing and shampooing.

Example XXIV

ί

The following paint preparation is prepared: 2-Methyl4-amino-5-nitro-N-1-dihydroxypropylaniline ...... 0.2 g (~ 3-Nitro-N-hydroxyethyl-4-amino) phenoxyethanol ... ......., 0.4 gi

Tetraaminoanthraquinone ....................., ......., ....... 0.3 g

Carboxymethyl cellulose .................. ,, ...........,.,., 2 g

Lauryl sulfate ............................... ······ ........ 5 gj 20Z Monoethanolamine solution in water ....... 0.1 g '

Hater as needed until ............... 100 g; pH 8.

When this mixture is applied for 20 min at 28 ° C to straw-yellow decolorized hair, after rinsing and shampooing, it imparts a chestnut color with red copper sheen.

Example XXV

They prepare the following paint formulation: 2-Isopropyl-4-amino-5-nitro-N-methylaniline.,., ......, ..., 1 µg 2- Methyl-6-nitraniline,.,., .., ....., .., ..., ............ ,, 0.1 g: 3-Nitro-N-methyl-4-amino-N '. N'-di-yl-hydroxyethylaniline ... 0.2 g Fropylene glycol. 10 g Carboxymethylcellulose ....., .. ,, .....,., .., ..., ......., .. 2 g |

Aramonium lauryl sulfate ........... ,,,, .... 5 g <4Z Ammonia solution ...., ............., ...... .,., ... ,,., .. 1 gy

Hater as needed until ....., ....., ....., ..................... 100 g pH 8.8. |

When this mixture is applied for 25 min. At 28 ° C to hair that has turned white, it gives this hair a clear red copper color after rinsing and shampooing.

Example XXVI

The following paint preparation is prepared: 2-Methyl-4-amino-5-nitro-N-aminoethylaniline .., .., .., .. 0.06 g / ~ N-methyl-3-amino-4 -nitro7phenoxyethanol .................. 0.3 g

Dihydrobromide of 3-nitro-N '-my thy 1-4-amino-N- "aminoethylaniline .........., ................ ............ 1.0.12 g of 2-Butoxyethanol ...... ............., ...... 8 g

Cellosize WP03 ........................................... 2 g

CetyldimethylhydroxyethylammoniumchToride ................ 2 g 20% Triethanolamine ............................ .......... 0 * 6 g

Water as needed until ......................., .............. 100 g pH 7.8.

When this mixture is applied to straw discolored hair for 25 min at 30 ° C, it rinses this hair a red copper color after rinsing and shampooing.

Example XXVII

The following paint preparation is prepared; 2-Methyl-A-amino-5-nitro-N - - - diethylaminoethylaniline 0.06 g N - / - - hydroxyethyl-2-amino-5-nitrophenol .... o.,., ...... ... ,, 0.19 g

Dihydrochloride of 3-nitro-N'-amino-1-4-amino-N, N-di-hydroxy-ethyl aniline ............ 0.13 g

Butyl glycol 8 g

Cellosize WP03 ....... ..... 0 ........., .. 00.0 ......,. 0.000. 2 g

Ce tyldimethylhydroxyethylammonium chloride .. 0 „2 g 20% Monoethanolamine solution in water 0.5 g

Water as needed until ...................................... 100 g pill 8.4.

When this mixture is applied to straw discolored hair for 30 min at 30 ° C, after rinsing and shampooing, it imparts a honey color with deep golden sheen.

Example XXVIII

The following paint preparation is prepared; 3- Nitro-4-amino-6-methyl-N- (1-hydroxypropyl) aniline ...... 0.2 g 2-Butoxyethanol ................ .......................... 10 g

Hydroxymethyl Cellulose ................................... 2 g

Cetyldimethylhydroxyethylammonium chloride ................ 2 g 20% Ammonia ............................ ................. 1 g

Water as needed until ...................................... 100 g pH 10.

When this mixture is applied to decolorized hair at room temperature for 30 minutes, it imparts a deep pink color to this hair.

Example XXIX

The following paint preparation is prepared: 3-Nitro-4-amino-6-methyl-N - - - aminopropylaninine ···· .. ··., 0.25 g of 2-Butoxyethanol .......... ................................ 5 g

Lauryl alcohol, oxyethylenated with 12 moles of ethylene oxide 5 g

Ammonia 22 ° B ............................................ Qf5 g

Water as needed until ...................................... 100 g pH 9.

When this mixture is applied to natural 90% white hair for 25 min at 28 ° C, it rinses this hair after rinsing and shampooing.

Preparation of (3-nitro-N 2 -hydroxyethyl-4-amino) phenyl - / -, - ^ dihy · -. droxypropyl ether, used in example XX.

This preparation proceeds according to the accompanying reaction scheme H.

0.2 mol or 39.6 g of 3-nitro-Ny ^ -hydroxyethyl-4-aminophenol are dissolved in 125 ml of 2N sodium hydroxide. 0.25 mol or 27.5 g of 1-chloropropanediol-2,3 are added to this solution, which has been preheated to about 90 ° C. Heating is continued for 2 hours. After cooling the reaction medium, it is extracted with ethyl acetate. After evaporation of the solvent to dryness, 29 g of the desired product are obtained in the form of orange crystals.

After recrystallization from isopropanol and drying under vacuum, the product melts at 102 ° C;

Preparation of (3-nitro-N wfl-hydroxyethyl-A-ainino) phenoxyethanol. used in examples XIX and XXIV. "

This preparation proceeds according to the accompanying reaction scheme I.

First stage

Preparation of / chloroethyl / "(2-nitro-7-hydroxy-A-ethoxy) phenyl-carbamate.

The starting material used is (3-nitro-A-amino) -phenoxyethanol, described in Example 1 of French patent 2,290,186.

A mill or 792 g (3-nitro-A-amino) -enoxyethanol is dissolved in 1600 ml of dioxane. 2.A mol or 2A0 g of calcium carbonate are added. The temperature is raised to about 90 ° C and then A, 8 moles or 686 g of chloroethyl chloroformate are added in small amounts with stirring. When everything is added, the mixture is heated at 90 [deg.] C. for a further 30 minutes. The reaction medium is filtered warm. The cooled filtrate is diluted with petroleum ether to precipitate the desired product, which melts at 119 ° C after recrystallization from dioxane and drying under vacuum.

Second stage

Preparation of (3-nitro-N-1-hydgoxyethyl-A-amino) phenoxyethanol.

0.1 mol or 30.05 g of chloroethyl / (2-nitro-hydroxy-A-ethoxy) phenylcarbaraate is added to 62 ml of water. 10 ml of 10N sodium hydroxide solution are added in small amounts in a few minutes with stirring. The temperature rises to about 60 ° C.

The temperature of the reaction medium is then raised to 70 ° C and then 20 ml of 10N sodium hydroxide solution are added with stirring. Stirring is continued for an additional 15 minutes at 70 ° C. After cooling, the desired product is filtered off, which melts at 82 ° C after washing with water, drying and recrystallization from methanol.

The various trade names used in the preceding examples have the following meanings: CARBOPOL 934 · Acrylic acid polymer of molecular weight 2 to 3 million, sold by Goodrich Chemical Company.

CEMULSOL NP ^: Nonylphenol with 4 moles of ethylene oxide sold by Rhone Poulenc.

CEMULSOL NP ^; Nonylphenol with 9 moles of ethylene oxide sold by Rhone Poulenc.

g ALFOL Cjg / jg (50/50): Cetylstaryl alcohol, sold by

Condéa.

Lanette E Wax: Partially sulfated cetylstearyl alcohol sold by Henkel.

CEMULSOL B: Ethoxylated castor oil sold by Rhone Poulenc.

MASQUOL: Sodium salt of diethylene triamine pentaacetic acid.

CELLOSIZE WP 03: Hydroxyethyl cellulose, sold by

Union Carbide.

REMCOPAL 334: Nonylphenol, oxyethylenated with 4 moles of ethylene oxide, sold by GERLAND.

REMCOPAL 349: Nonylphenol, oxyethylenated with 9 moles of ethylene oxide, sold by GERLAND.

Claims (3)

Benzene series nitro derivative, characterized in that it is (3-nitro-N-B-hydroxyethyl-4-amino) phenyl-β, γ-dihydroxypropyl ether. 2. Benzene series nitro derivative, characterized in that it is (3-nitro-N-B-hydroxyethyl-4-amino) phenoxyethanol. 3. Keratin fiber dyeing composition, characterized in that it contains at least one compound as defined in claim 1 or 2.