CH651469A5 - TINCTORIAL COMPOSITION FOR KERATINIC FIBERS BASED ON NITRO-3 ORTHOPHENYLENEDIAMINES, NITRO-3 ORTHOPHENYLENEDIAMINES USED AND THEIR PREPARATION METHODS. - Google Patents

Description

The present invention therefore relates to dye compositions for keratin fibers containing nitro-3-orthophenyl-enediamines.

Another object of the invention is constituted by the new 3-nitro-orthophenylenediamines used in accordance with the invention, as well as their methods of preparation.

Other objects of the present invention will become apparent on reading the description and examples which follow.

The dye compositions for keratin fibers in accordance with the invention are essentially characterized in that they contain, in a suitable solvent medium for dyeing keratin fibers, at least one dye corresponding to formula I:

MHR2 45

O.N \ Jy NHR

t

Z

(I)

50

in which R 1 and R 2 denote, independently of each other, a hydrogen atom, an alkyl group, a mono- or polyhydroxylated alkyl group, an alkyl group substituted by an alkoxy group, an aminoalkyl group, the amino group of which may optionally being mono- or disubstituted by an alkyl group, the radical R2 may also denote a phenyl group, or phenyl substituted by an alkyl, hydr-oxyl or amino group, Z denotes a hydrogen atom or an alkyl group.

In the above formula, the alkyl radical preferably denotes a radical having from 1 to 4 carbon atoms and the alkoxy group preferably denotes methoxy or ethoxy.

Among the more particularly preferred groups, there may be mentioned for R2 a hydrogen atom, a methyl group,

ethyl, propyl, butyl, a p-hydroxyethyl group, a ß-hydroxypropyl group, a ß, y-dihydroxypropyl group, an N, N-diethylaminoethyl group, a p-hydroxy-phenyl group, or a ß-methoxyethyl group, for Rj a hydrogen atom, a methyl, ethyl, β-hydroxyethyl group and for Z a hydrogen atom and a methyl group.

The compounds giving particularly advantageous results in the context of the present invention correspond to formula I in which Z necessarily denotes a methyl group. Other compounds giving particularly appreciable results are those for which R2 is different from hydrogen and denotes in particular methyl or β-hydroxyethyl. These compounds in particular have good safety.

These compounds can also be used in the form of their cosmetically acceptable salts, for example in the form of hydrochloride, sulfate, etc.

The preferred compounds used in accordance with the invention make it possible to obtain copper shades more or less rich in red ranging from 7.5 YR to 10 R according to the Munsell evaluation.

The shade is designated by H in the Munsell notation according to which a color is defined by the formula HV / C in which the three parameters respectively designate the shade or hue (H), the intensity or value (V) and the purity or chromaticity (C), the slash being a simple convention.

With regard to the Munsell notation, reference may be made to the publication of "Officiai Digest", April 1964, pp. 373-377.

Among the compounds used in accordance with the invention, the compounds of formula II:

NHR ',

(II)

ojnv / \ / nhr ',

V

in which R'x and R'2 denote independently of each other a hydrogen atom, an alkyl group, a mono- or polyhydroxylated alkyl group, an alkyl group substituted by an alkoxy group, an aminoalkyl group the amino group can optionally be mono- or disubstituted by an alkyl group, the radical R'2 can also denote a phenyl or phenyl group substituted by an alkyl, hydroxyl or amino group, and Z 'denotes a hydrogen atom or an alkyl group provided that R'j, R'2 and Z 'cannot simultaneously denote hydrogen, when R'2 denotes methyl or phenyl R't and Z' cannot both denote hydrogen simultaneously, when Z 'denotes methyl one at least groups R't or R'2 is different from hydrogen, when R't and R'2 denote methyl Z 'is different from hydrogen, and their cosmetically acceptable salts are new.

The process for the preparation of these compounds which constitutes another subject of the invention consists, as regards the compounds of formula I for which Rj denotes hydrogen, in effecting a selective reduction of the compounds of formula III:

NHR'2 0, N \ J \ / NO,

Y

z

(in)

the selective reduction being carried out either using the alkali sulfite according to M. Kamel, M.I. Ali and M.M. Kamel, "Tetrahedron", 1966, vol. 22, p. 3353, either by hydrogen transfer from cyclohexene to the compound of formula III in the presence of palladium on carbon

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as a catalyst according to Ian D. Entwitstle, Robert A. W Johnstone and T. Jefferey Povall, "JCS Perkin", I, 1975, p. 1300.

The compounds of formula I for which Rj denotes alkyl or substituted alkyl can be obtained by benzenesulfonation or selective paratoluenesulfonation of the compounds of formula I for which R! denotes hydrogen. A haloalkane of formula XRx, in which X denotes a halogen atom and Rj alkyl or substituted alkyl, is then reacted on the arylsulfon-amides thus obtained, then, after substitution, the sulfonamides are hydrolyzed.

The reaction scheme can essentially be summarized as follows:

nhr,

nhr,

02n \ / \ / nh2 ► ojn \ / \ / nhso2- <> -r3

z nhr2

z

0 * n \ / \ / n-S02- <^ -Ra ^ O.N ^^ / X / NHRj

R3 = H or CH3 NHR,

z

R.

1

z

A number of the intermediate compounds of formula III used in accordance with the process of the invention are known in themselves. In general, these compounds of formula III can be obtained by the action of ammonia or amines of formula R2NH2, in which R2 has the same meaning as that indicated above, on the dinitrated, chlorinated or methoxylated compounds. taking advantage of the mobility of the chlorine atom or of the methoxy group.

The compositions in accordance with the invention can be used for the direct dyeing of keratin fibers or for the oxidation dyeing of these fibers, in which case the compounds of formula I confer reflections complementary to the basic dye obtained by oxidative development of the precursors oxidation dyes. These compositions contain the compounds of formula I in proportions of between 0.001 and 5% by weight and preferably between 0.01 and 3% by weight relative to the total weight of the dye composition.

They can contain anionic, cationic, nonionic, amphoteric surfactants or their mixtures. These surfactants are present in the compositions of the invention in proportions of between 0.5 and 55% by weight and preferably between 4 and 40% by weight relative to the total weight of the composition.

The cosmetic vehicle generally consists of water and organic solvents can also be added to the compositions to dissolve compounds which are not sufficiently soluble in water. Among these solvents, mention may be made of lower alkanols such as ethanol and isopropanol, polyols such as glycerol, glycols or glycol ethers such as 2-butoxyethanol, ethylene glycol, monoethyl ether. ethylene glycol, propylene glycol, monoethyl ether and monoethyl ether of diethylene glycol as well as analogues and their mixtures. These solvents are preferably present in proportions ranging from 1 to 75% by weight and in particular from 5 to 50% by weight relative to the total weight of the composition.

The compositions can preferably be thickened with the compounds chosen from sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and various polymers having the thickener function such as more particularly acrylic acid derivatives. It is also possible to use mineral thickening agents such as bentonite. These thickening agents are preferably present in proportions of between 0.5 and 10% by weight and in particular between 0.5 and 3% by weight relative to the total weight of the composition.

The compositions according to the invention can also contain various adjuvants usually used in hair dye compositions and in particular penetration agents, sequestering agents, film-forming agents, buffers, preservatives and perfumes.

These compositions can be in various forms such as liquids, creams, gels or any other form suitable for dyeing the hair. They can also be packaged in aerosol bottles in the presence of a propellant.

The pH of these dye compositions can be between 3 and 11.5, preferably between 5 and 11.5. It is adjusted to the desired value using an basifying agent such as ammonia, sodium carbonate, potassium or ammonium, sodium or potassium hydroxides, alkanoamines such as mono -, di- or triethanolamine, alkylamines such as ethylamine or triethylamine or using an acidifying agent such as phosphoric, hydrochloric, tartaric, acetic, lactic or citric acids.

When the compositions are intended to be used in a direct hair coloring process, they may contain, in addition to the compounds according to the invention, other direct dyes such as azo or anthraquinone dyes, for example tetraminoanthraquinone, nitro dyes of the benzene series different from the compounds of formula I and more particularly the following compounds:

2-methyl-6-nitro aniline,

3-nitro-4-amino phenol,

nitro-3 N-p-hydroxyethylamino-4 phenol,

35 3-nitro-4-amino-6-methylphenol,

3-amino-4-nitro phenol,

2-amino-3-nitro phenol,

nitro-3, N-P-hydroxyethylamino-6 anisole, N-ß, y-dihydroxypropylamino-3 nitro-4 anisole, 40 le (N-methylamino-3, nitro-4) phenoxyethanol,

(N-methylamino-3, nitro-4) phenyl, p, y-dihydroxypropylether, N, N '(- p-hydroxyethyl) nitroparaphenylenediamine,

nitro-3, N'-methylamino-4, N, N- (di-P-hydroxyethyl) aniline, methyl-2 amino-4 nitro-5 N-P-hydroxyethylaniline,

45 methyl-2 amino-4 nitro-5 N-P-diethylaminoethylaniline, methyl-2 amino-4 nitro-5 N-methylaniline.

The concentrations of these direct dyes other than the dyes of formula I can be between 0.001 and 5% by weight relative to the total weight of the composition.

These compositions are applied to the keratin fibers for an exposure time of 5 to 70 min, then the fibers are rinsed, optionally washed, rinsed again and dried.

These compositions can also be used in the form of a hair styling lotion intended at the same time to give the hair a light coloring and to improve the staying power of the styling. In this case, they are in the form of aqueous, alcoholic or hydroalcoholic solutions containing at least one cosmetic resin and their application is carried out on damp hair previously washed and rinsed which are possibly coiled and then dried.

The cosmetic resins used in the setting lotions may in particular be polyvinylpyrrolidone; crotonic acid / vinyl acetate, vinylpyrrolidone / vinyl acetate, semi-esters of maleic anhydride / vinyl butyl-65 ether and maleic anhydride / methyl vinyl ether copolymers as well as any other cationic, nonionic or amphoteric polymer usually used in this type of compositions. These cosmetic resins are used in the compositions of the invention at a rate of 1 to 3% by

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weight and preferably from 1 to 2% by weight based on the total weight of the composition.

When the compositions constitute oxidation dyes, the compounds of formula I in accordance with the invention are essentially used with a view to providing reflections to the final dye.

These compositions then contain, in combination with at least one nitrated dye of formula I, dye precursors by oxidation.

They may contain, for example, para-phenylenediamines such as: para-phenylenediamine, paratoluylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-dimethyl-3-methoxy-3 para-phenylenediamine, N - ^ - methoxyethyl) para-phenylenedediamine, N , N-di (P-hydroxyethyl) amino-4 aniline, N, N- (ethyl, carbamylmethyl) amino-4 aniline and their salts.

They can also contain paraaminophenols, for example: paraaminophenol, N-methylparaaminophenol, chloro-2 amino-4 phenol, chloro-3 amino-4 phenol, methyl-2 amino-4 phenol and their salts.

They can also contain heterocyclic derivatives, for example: diamino-2,5 pyridine, N, N-diethylamino-5 amino-2 Pyridine, amino-7 benzomorpholine, amino-2 hydroxy-5 pyridine.

The compositions according to the invention may contain, in association with the precursors of dyes by oxidation of the para type, couplers well known in the state of the art.

As couplers, there may be mentioned in particular: metadiphenols such as resorcinol, 2-methyl resorcinol, metaaminophenols such as: metaaminophenol, 2-methyl-5-amino phenol, 2-methyl-N- (P-hydroxyethyl ) 5-amino phenol, 6-hydroxy benzomorpholine and their salts, metaphenylenediamines such as: (2,4-diamino) phenoxyethanol, 2,4-diamino phenyl ß-amino-ethyl ether, 6-amino benzomorpholine , [N - ^ - hydroxyethyl) -2-amino-4] phenoxyethanol, (diamino-2,4) -phenyl ß, y-dihydroxypropylether and their salts, metaacylaminophenols, meta-ureidophenols, metacarbalcoxyaminophenols such as : 2-methyl-5-acetylamino-phenol, 2-methyl-5-ureido-phenol, 2-methyl-5-carbethoxyamino-phenol.

Finally, other couplers which can be used in the compositions of the invention may be mentioned: a-naphthol, couplers having a methylene actil group such as diketo-nic compounds and pyrazolones and heterocyclic couplers such as diamino-2, 4 pyridine, and their salts.

These compositions contain, in addition to dye precursors by oxidation, reducing agents such as more particularly sodium sulfite, thioglycolic acid, thiolactic acid, sodium bisulfite, ascorbic acid and hydroquinone. These reducing agents are present in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition. The dye precursors by oxidation can be used in the compositions of the invention at concentrations of between 0.001 and 5% by weight and preferably between 0.03 and 2% by weight based on the total weight of the composition. The couplers can also be present in proportions of between 0.001 and 5% by weight, preferably between 0.015 and 2% by weight. Their pH is preferably between 7 and 11.5 and is adjusted using basifying agents defined above.

The licensee found that the compounds according to the invention were particularly stable in such compositions.

The process for dyeing keratin fibers, in particular human hair, using revelation by an oxidant, consists in applying to the hair the dye composition comprising both a dye according to the invention and the dye precursors by oxidation and to develop the coloring using an oxidizing agent present in the dye composition or else applied to the hair in a second step.

The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide and persalts. In particular, a solution of hydrogen peroxide at 20 volumes is used.

Once the composition with the oxidizing agent has been applied to the keratin fibers, it is left to stand for 10 to 50 min, preferably 15 to 30 min, after which the keratin fibers are rinsed, they are optionally washed with shampoo , they are rinsed again and dried.

The examples which follow are intended to illustrate the invention without being limiting in nature.

Example 1:

The following dye composition is prepared:

Amino-2 nitro-3 methyl-5 N-methylaniline 0.9 g

Butoxy-2 ethanol 10 g

AlfolCl & 1, (50/50) 8 g

Lanette wax 0.5 g

Cemulsol B. 1 g

Oleic diethanolamide 1.5 g

Triethanolamine 1 g

Water q.s.p. 100 g This composition has a pH of 9.

This mixture applied 25 min at 28 ° C to bleached hair gives them, after rinsing and shampooing, a coloration of 2.0 YR 5.5 / 8 according to Munsell.

The compositions mentioned in Table 1 are prepared in the same manner as that indicated above, the support being the same as that used in Example 1, the basifying agent being specified as well as the pH, the dyeing conditions such as the temperature, rinsing and washing being similar to those indicated in Example 1, an amount of water sufficient for 100 g of composition is always added.

By applying the composition of Example 2 to the naturally white hair at 90% previously permed and by proceeding in the same way, there is a coloration of 7.5 YR 6/8 according to Munsell identical to that observed on naturally hair. 90% white, dyed under the same conditions.

(Table at the top of the next column)

Example 10:

The following dye composition is prepared:

Amino-2, nitro-3, methyl-5, N-methylaniline 0.5 g

Nitro-3, N'-methylamino-4, N ^ -aminoethylaniline 0.1 g

(N-methylamino-3, nitro-4) -phenoxyethanol 0.28 g

Ethanol at 96 ° 5 g

Propylene glycol 5 g

Diethanolamides of coconut fatty acids 2.2 g

Lauric acid 0.8 g

Ethylene glycol monoethyl ether 2 g

Monoethanolamine 1.1g

Water q.s.p. 100 g pH 10.5.

This mixture applied 25 min at 30 ° C to hair bleached in white gives them, after rinsing and shampooing, a light red copper coloring.

Example 11:

The following dye composition is prepared:

Amino-2, nitro-3, methyl-5 aniline 0.5 g

Nitro-3, N ^ -hydroxyethylamino-4 phenol 0.15 g

Tetraaminoanthraquinone 0.10 g

Butoxy-2 ethanol 10 g

Cémulsol NP4 12 g

Cémulsol NPp 15 g

Oxyethylenated oleic alcohol with 2 mol of ethylene oxide 1.5 g

Oxyethylenated oleic alcohol with 4 mol of ethylene oxide 1.5 g

Triethanolamine 2 g

Water q.s.p. 100 g pH 9.

This mixture applied 35 min at 30 ° C to hair bleached with straw blonde gives them, after rinsing and shampooing, a medium coppery brown coloring.

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Example 12:

The following dye composition is prepared:

Nitro-3 orthophenylenediamine 0.3 g Nitro-3, N'-methylamino-4, N, N-di-P-hydroxyethylaniline 0.11 g

5 N, N'-P-hydroxyethylnitroparaphenylenediamine 0.11 g

96 ° alcohol 10 g

Carboxymethylcellulose 2 g

Ammonium lauryl sulfate 5 g

Monoethanolamine 2 g

10 Water q.s.p. 100 g pH 10.5.

This mixture applied 25 min at 30 ° C on bleached hair with straw blonde gives them, after rinsing and shampooing, a very coppery brown coloring.

Example 13:

The following dye composition is prepared:

N-butylamino-2 nitro-3 methyl-5 aniline 0.3 g 20 Nitro-3, N'-methylamino-4, N, N-di-P-hydroxyethylaniline 0.05 g

Butoxy-2 ethanol 10 g

Diethanolamides of coconut fatty acids 2.2 g

Lauric acid 0.8 g

Ethylene glycol monoethyl ether 2 g

25 Monoethanolamine 1 g

Water q.s.p. 100 g pH 8.5.

This mixture applied 30 min at 28 ° C to hair bleached in white gives them, after rinsing and shampooing, a light beige coloring 30 with golden reflections.

Example 14:

The following dye composition is prepared:

N-p-diethylaminoethylamino-2 nitro-3

35 5-methyl aniline 1 g

Butoxy-2 ethanol 5 g

Lauric alcohol with 10.5 mol of ethylene oxide 5 g

Ammonia at 22 ° B 1 g

Water q.s.p. 100 g 40 pH 9.

This dye composition applied 25 min at 28 ° C on bleached hair gives them, after rinsing and shampooing, a coloring 6.5 YR 5/10 according to Munsell.

45 Example 15:

The following dye composition is prepared:

N-ß-hydroxypropylamino-2 hydrochloride

3-nitro-5-methyl aniline 0.5 g

Propylene glycol 10 g

50 Carboxymethylcellulose 10 g

Monoethanolamine 5 g

Water q.s.p. 100g

This mixture applied 25 min at 30 ° C to hair bleached with white gives them, after rinsing and shampooing, a coloring 55 4 YR 7/7 according to Munsell.

Example 16:

The following dye composition is prepared:

N-ß, y-dihydroxypropylaminor2 hydrochloride

60 3-nitro-5-methyl aniline 1.82 g

Nitro-3, N-P-hydroxyethylamino-4 phenol 0.3 g Nitro-3, N'-methylamino-4, N, N-di-ß-hydroxy-

ethylaniline 0.5 g

Butoxy-2 ethanol 10 g

65 Monoethanolamide of lauric acid 1.5 g

Lauric acid 1 g

Hydroxyethylcellulose 5 g

Monoethanolamine 4 g

7

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Water q.s.p. 100 g pH 10.

This mixture applied 25 min to 30; C on naturally white hair at 90% gives them a light brown red copper color.

Example 17:

The following dye composition is prepared: N-P-2-methoxyethylamino-3-nitro-5-methyl-aniline 0.6 g

Butoxy-2 ethanol 10 g

Carbopol 934 2 g

Monoethanolamine 2 g

Water q.s.p. 100 g pH 8.8.

This dye composition applied 30 min at 30 ° C on bleached hair gives them, after rinsing and shampooing, a color 7.5 YR 7/6 according to Munsell.

Example 18:

The following dye composition is prepared:

N-ß-hydroxypropylamino-2 hydrochloride

3-nitro-5-methyl aniline 1 g

Paraphenylenediamine 0.25 g

Paraaminophenol 0.065 g

0.2 g resorcin

Metaaminophenol 0.08 g

2-methyl, N-P-hydroxyethylamino-5 phenol 0.05 g

Butoxy-2 ethanol 8 g

Carboxymethylcellulose 2 g

Ammonium lauryl sulfate 5 g

Ammonium acetate 1 g

Propylene glycol 8 g

Masquol DTPA 2 g

Thioglycolic acid 0.4 g

Ammonia at 22 ° B 10 g

Water q.s.p. 100 g pH 10.6.

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

This mixture applied 30 min at 30 ° C to bleached straw blonde hair gives them, after rinsing and shampooing, a medium brown color with copper highlights.

Example 19:

The following dye composition is prepared:

Amino-2, nitro-3 methyl-5 aniline 0.8 g

Paraphenylenediamine 0.18 g

Paraaminophenol 0.05 g

Resorcin 0.12 g

Metaaminophenol 0.115 g

2,4-diamino dihydrochloride phenoxyethanol 0.03 g

Cémulsol NP4 12 g

Cémulsol NP9 15 g

Oleic alcohol with 2 mol of ethylene oxide 1.5 g

Oleic alcohol with 4 mol of ethylene oxide 1.5 g

Propylene glycol 6 g

Trilon B 0.12 g

Ammonia at 22nd B 11g

Thioglycolic acid 0.6 g

Water q.s.p. 100 g pH 10.5.

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

This mixture applied at 30 min at 30 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a medium coppery brown coloring.

Example 20:

The following dye composition is prepared:

N-p-diethylaminoethylamino-2 nitro-3

5-methyl aniline 1.5 g Nitro-3, N'-methylamino-4, N, N-di-ß-hydroxy-

0.2 g ethylaniline

Butoxy-2 ethanol 10 g

Carboxymethylcellulose 10 g

Monoethanolamine 5 g

Water q.s.p. 100 g pH 10.

This mixture applied 30 min at 30 ° C to hair bleached with white gives them, after rinsing and shampooing, an ashy beige coloring.

Example 21:

The following dye composition is prepared:

N-p-hydroxyethylamino-2 nitro-3 methyl-5 aniline 1.2 g

Butoxy-2 ethanol 10 g

Monoethanolamide of lauric acid 1.5 g

Lauric acid 1 g

Hydroxyethylcellulose 5 g

Monoethanolamine 2 g

Water q.s.p. 100 g pH 10.

This mixture applied 25 min at 28 ° C to hair bleached in white gives them, after rinsing and shampooing, a coloring 5 YR 8/6 according to Munsell.

Example 22:

The following dye composition is prepared:

N ^ -hydroxyethylamino-2 nitro-3 methyl-3 aniline 1.21 g

Paraphenylenediamine 0.5 g

0.1 g resorcin

Metaaminophenol 0.21 g

Orthoaminophenol 0.17 g

Carbopol 934 1.5 g

96 ° alcohol 11 g

Butoxy-2 ethanol 5 g

Trimethylethylammonium bromide 1 g

Trilon B 0.1 g

Ammonia at 22 ° B 10 g

Thioglycolic acid 0.2 g

Water q.s.p. 100 g pH 10.5.

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

This mixture applied 25 min at 28 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a dark brown coloring with copper highlights.

Example 23:

The following dye composition is prepared:

Nitro-3 orthophenylenediamine 0.5 g

2-methyl, 6-nitro aniline 0.2 g

Paraphenylenediamine 0.08 g

2-methyl resorcin 0.045 g

Metaaminophenol 0.06 g

Cémulsol NP4 21 g

Cémulsol NP9 24 g

Oleic acid 4 g

Butoxy-2 ethanol 3 g

Ethanol at 96 ° 10 g

Masquol DTPA 2.5 g

Sodium bisulfite solution at 35 ° B 1 g

Ammonia at 22 ° B 10 g Water q.s.p. 100 g pH 11.

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At the time of use, 80 g of hydrogen peroxide are added to 20 volumes.

This mixture applied 25 min at 30 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a very golden dark blond coloring.

The following examples are intended to illustrate the processes for preparing the new compounds used in accordance with the invention.

Preparation example 1:

Preparation of N-butylamino-2, nitro-3, methyl-5 aniline

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a) Preparation of 2,6-dinitro-4-methyl-N-butylaniline

0.05 mol (10.8 g) of 2,6-dinitro-4-methyloblorobenzene in 25 ml of butylamine is added little by little, with stirring, over 10 minutes, cooling the reaction medium if necessary so as not to exceed 50 ° C. When the addition is complete, stirring is continued for 5 min, then the reaction medium is poured into 100 ml of ice water. The expected product precipitates, it is drained, washed with water and recrystallized from ethanol. After drying under vacuum, it melts at 52 ° C.

Analysis for CnH ^ NjO ^

Calculated: C 52.17 H 5.93 N 16.60 0 25.30%

Found: C 52.13 H 6.04 N 16.59 O 25.34%

b) Preparation of N-butylamino-2, nitro-3, methyl-5 aniline

0.041 mol (10.4 g) of 2,6-dinitro-4-methyl-N-butylaniline is added to 50 ml of ethanol supplemented with 10.8 g of cyclohexene and 2.8 g of Pd / C at 10%. The reaction medium is brought to reflux for 1 h, then it is filtered hot to remove the catalyst. The filtrate is cooled to -15 ° C. The expected product crystallizes. It is wrung, washed with a little iced alcohol and dried under vacuum. It melts at 68 ° C.

Analysis for C11II17N302: Calculated: C 59.19 H 7.62 Found: C 59.33 H 7.75

N 18.83 O 14.35% N 18.98 O 14.44%

a) Preparation of 2,6-dinitro-methyl-4 N-fi-methoxyethylaniline

0.05 mol (10.8 g) of 2,6-dinitro-4-methyloblorobenzene in 25 ml of methoxyethylamine is added little by little, with stirring, over 10 min, while cooling the reaction medium if necessary. not exceed 50 ° C. When the addition is complete, stirring is continued for 5 min, then the reaction medium is poured into 100 ml of ice water. The expected product precipitates. It is drained, washed with water and recrystallized from ethanol. After drying under vacuum, it melts at 75 ° C.

Analysis for C10H13N3Os:

Calculated: C 47.06 H 5.13 O 31.34 N 16.47% 40 Found: C 47.08 H 4.99 0 31.07 N 16.50%

b) Preparation of N-methoxyethylamino-2, nitro-3, methyl-5 aniline

0.03 mol (7.65 g) of 2,6-dinitro, 4-methyl, N-ß-45 methoxyethylaniline is dissolved in 38 ml of absolute alcohol containing 12.3 g of cyclohexene and 3.8 g of Pd / C at 10%. Then the alcoholic solution is brought to reflux for 15 min. The hot reaction medium is filtered to remove the catalyst and then, after cooling, 15 ml of alcohol saturated with hydrochloric gas are added. The expected product precipitates 50 in the form of the hydrochloride. The hydrochloride is drained and washed with a little alcohol, then it is dissolved in water. This aqueous solution is made alkaline with ammonia to precipitate the expected product which is drained, washed with water and recrystallized from ethanol; it melts at 71 ° C.

55 Analysis for C10H15N3O3:

Calculated: C 53.33 H 6.67 N 18.67 0 21.33%

Found: C 53.46 H 6.70 N 18.55 O 21.27%

^ Preparation example 3:

Preparation of nitro-2, methyl-4, amino-6 hydroxy-4 'diphenyl-amine ^

02n \ j \ / n02

Preparation example 2:

Preparation of N ^ -methoxyethylamino-2, nitro-3, methyl-5 aniline h, c — c 7 — nh — k 7 — oh r: H,

V

ch

9

651,469

oh y>

nh

„3rd - <^> - nh-t / ^> - oh

W02

m2

a) Preparation of 2,6-dinitro-4-methyl, 4-hydroxy-diphenylamine

The mixture is heated under reflux for 2 h 0.1 mol (10.9 g) of paraaminophenol and 0.05 mol (10.83 g) of 2,6-dinitro-4-methylchlorobenzene in 60 ml of alcohol. After cooling the reaction medium, the 2,6-dinitro-methyl-4, hydroxy-4 'diphenylamine is filtered off and washed with alcohol. After recrystallization from alcohol and drying under vacuum, the product melts at 192: C.

b) Preparation of nitro-2, methyl-4, amino-6 hydroxy-4 'diphenylamine

After adding 0.038 mol (11 g) of 2,6-dinitro-4-methyl, 4-hydroxy-diphenylamine to 200 ml of alcohol supplemented with 20 ml of ammonia at 22e B, hydrogen sulfide is bubbled for 30 min in this solution. The reaction medium is then brought to reflux for 2 h. The alcoholic solution is filtered after cooling, then evaporated to dryness under vacuum. The residue is taken up in 150 ml of 2N hydrochloric solution. It is filtered to remove the insoluble material, then the filtrate is made alkaline with ammonia. The expected product precipitates. It is drained, washed with water, then recrystallized from ethanol; it melts at 163; vs.

Analysis for C2 3II] jN303:

Calculated; C 60.23 H 5.02 N 16.22 0 18.53%

Found: C 60.03 H 5.11 N 16.25 0 18.55%

Preparation example 4:

Preparation of N ^ -hydroxyethylamino-2, nitro-3, methyl-5 aniline nii-ch2oh2oh

OîNN ^ X / NHJ

a) Preparation of 2,6-dinitro-methyl-4, N ^ -hydroxyethylaniline

0.35 mol (76 g) of 2,6-dinitro-4-methyloblorobenzene in 150 ml of ethanolamine is added little by little, with stirring, over 10 minutes, cooling the reaction medium if necessary so as not to exceed 5 75 ° C. When the addition is complete, stirring is continued for 5 min, then the reaction medium is poured into 600 g of ice water. The expected product precipitates. It is drained, washed with water, then recrystallized from ethanol. After drying under vacuum, it melts at 131 ° C.

10 Analysis for CpHj iN305:

Calculated: C 44.81 H 4.56 N 17.43 0 33.20%

Found: C 44.93 H 4.49 N 17.32 0 33.00%

b) Preparation of N-ß-hydroxyethylamino-2, nitro-3, methyl-5 I5 aniline

After adding 0.4 mol (96.4 g) of 2,6-dinitro-methyl-4, N-ß-hydroxyethylaniline to 1500 ml of absolute alcohol supplemented with 160 ml of ammonia at 22 ° B, bubbled hydrogen sulfide for 30 min in this alcoholic solution. The temperature rises to 50 ° C., then falls again. The bubbling is then stopped, then the reaction medium is brought to reflux for 1 hour. After concentrating the alcoholic solution to 300 ml, the mineral salts are filtered. The filtrate is then evaporated to dryness. The residue obtained in the form of a red oil is redissolved in 80 ml of ethanol at 96 °. After the addition of 170 ml of hydrochloric ethanol (to 7 mol of hydrochloric acid per liter of alcohol) and cooling to 0 ° C., the expected product is drained, which precipitated in the form of the hydrochloride. After washing with alcohol , this hydrochloride is dissolved in 300 ml of water. By neutralizing this solution with ammonia, the N ^ -hydroxyethylamino-2, 3-nitro, 5-methyl aniline is precipitated. product, washed with water and then recrystallized from alcohol at 96 ° C. After drying under vacuum, it melts at 96 ° C.

Cl

02N \ Y / kN / N02

V

Analysis for C9H13N303: Calculated: C 51.18 H 6.16 Found: C 51.09 H 6.21

N 19.91 O 22.75% N 20.06 O 22.75%

40

Preparation example 5

Preparation of amino-2, nitro-3, methyl-5 N ^ -hydroxyethylaniline nh,

02n \ s / \ / n1i-ch2ch20h ► oznsy '/ nh

45

Y

ch.

nh.

Tosyl

0 »N \ ^ \ / N - Tosyl ch.

ch3

nh-ch2ch20h ch2ch2oiî

h2n-ch2ch2oh o2n \ / \ / no2

V

NH,

• ° 2N '

ch3

nh-ch2ch20h v

ch nh - ch2 ~ ch2oh o2n \

V

ch.

ch.

65 a) Preparation of amino-2, nitro-3, methyl-5 N-fi-hydroxyethyl, N-tosylaniline

0.087 mol (28 g) of amino-2, nitro-3, methyl-5, N-tosylaniline are dissolved in 85 ml of DMF previously heated in a bath.

651,469

10

marie boiling. 9.7 g of quicklime are then added and then, over 30 min, 0.174 mol (21.75 g) of glycol bromhydrin is gradually introduced with stirring, while maintaining the heating in a boiling water bath. After 1% at h, the hot reaction medium is filtered, then the filtrate is poured into 250 ml of ice water. The expected product precipitates. It is wrung, washed with water and dried under vacuum. After recrystallization from acetic acid and drying under vacuum, it melts at 201 ° C.

Analysis for C16H19N305S:

Calculated: C 52.60 H 5.21 Nile, 51 O 21.92 S 8.77%

Found: C 52.47 H 5.14 NI 1.41 0 21.82 S 8.68%

b) Preparation of amino-2, nitro-3, methyl-5 N-ß-hydroxy-

ethylaniline

0.0458 mol (16.7 g) of amino-2, nitro-3, methyl-5, NP-hydroxyethyl, N-tosylaniline are introduced with stirring in 167 ml of concentrated sulfuric acid added with 48 ml of water . The mixture is heated for 1 hour in a boiling water bath, then poured over 850 g of crushed ice. The sulfuric solution is neutralized using ammonia. The expected product precipitates. After spinning, washing with water, drying under vacuum and recrystallization from ethanol, it melts at 166 ° C.

Analysis for CgH1303N3:

Calculated: C 51.18 H 6.16 N 19.91 O 22.75%

Found: C 50.93 H 6.20 N 19.85 O 22.68%

Preparation example 6:

Preparation of amino-2, nitro-3, methyl-5, N-methylaniline NHj - NH2

OiNN / VN ":" ° 2N \ / \ / NH r |, ° syl

NH,

o2N \ / \ / ^ ~ Tosy1

in"

¥ V

V

NH CUcii.

a) Preparation of amino-2, nitro-3, methyl-5, N-tosylaniline

0.15 mol (25.05 g) of amino-2, nitro-3 and 5-methyl aniline are dissolved in 75 ml of pyridine, then added gradually, with stirring, between 40 and 45 ° C, 0.165 mol (31.4 g) of paratoluenesulfo-chloride. When the addition is complete, stirring is continued for 1 hour at 45 ° C., then the reaction medium is poured into 450 ml of ice water and neutralizes the pyridine using hydrochloric acid. The expected product which has precipitated is filtered off, washed with water and then recrystallized using acetic acid. After drying under vacuum, it melts at 184 ° C.

Analysis for C14HlsN304S:

Calculated: C 52.34 H 4.67 N 13.08 O 19.94 S 9.97%

Found: C 52.33 H 4.69 N 12.89 0 19.86 S 10.12%

b) Preparation of amino-2, nitro-3, methyl-5, N-methyl, N-tosylaniline

0.246 mol (79 g) of amino-2, nitro-3, methyl-5 N-tosylaniline is dissolved in 260 ml of normal sodium solution at 40 ° C. 0.286 mol (30 h) is added gradually over 3 hours. ml) of methyl sulphate, maintaining the temperature in the vicinity of 40 ° C. Towards the end of the addition of methyl sulphate, the pH of the alkaline reaction medium is maintained by simultaneously adding 20 ml of normal sodium solution. After cooling to around 10 ° C, the expected product is drained and precipitated. It is washed with a normal sodium solution and then with water and it is recrystallized using acetic acid. After drying under vacuum, it melts at 208 ° C.

Analysis for C! 5H17N304S:

Calculated: C 53.73 H 5.07 N 12.54 0 19.10 S 9.55% Found: C 53.81 H 5.11 N 12.39 0 19.01 S 9.41%

c) Preparation of amino-2, nitro-3, methyl-5 N-methylaniline

In 354 ml of concentrated sulfuric acid added with 60 ml of water and previously heated to 90 ° C, 0.1785 mol (59.8 g) of amino- is added gradually, with stirring in 1% h 2, nitro-3, N-methyl, N-tosylaniline. Heating is continued for another 15 min, then the reaction medium is poured into 1.5 kg of ice water. The expected product precipitates in the form of sulfate. We wring it out, wash it with a little ice water. The sulfate is suspended in water and, by addition of ammonia with stirring, the amino-2, nitro-3, methyl-5, N-methylaniline are released which, after spinning, washing with water and vacuum drying, bottom at 113 "C.

Analysis for Cgl ^! N302:

Calculated: C 53.04 H 6.08 N 23.20 0 17.68%

Found: C 53.12 H 6.13 N 23.14 0 17.54%

Preparation example 7;

Preparation of amino-2, nitro-3, N-methylaniline

30

40

wh „

50

° 2n x / n / "" ch3

V

a) Preparation of amino-2, nitro-3, N-tosylaniline

0.1 mol (15.3 g) of 3-nitrophenylenediamine is dissolved in 50 ml of pyridine, then 0.11 mol (21 g) of paratoluenesulfochloride is added gradually, with stirring, between 40 and 45 ° C. . When the addition is complete, stirring is continued for 15 min, then the reaction medium is poured into 250 ml of ice water. The expected product precipitates. It is wrung, washed with water and recrystallized using acetic acid. It melts at 195 ° C.

b) Preparation of amino-2, nitro-3, N-methyl N-tosylaniline

0.093 mol (28.5 g) of amino-2, nitro-3, N-tosylaniline are dissolved in 112 ml of normal sodium solution at 30 ° C. Is added little by little, with stirring, in A h, 0.122 mol (15.45 g) methyl sulfate. The temperature is maintained between 35 and 40 ° C. Towards the end of the addition of the methyl sulphate, 3 ml of 10N sodium solution are gradually added simultaneously in order to maintain the alkaline pH.

The reaction medium is cooled, then the expected product which is precipitated is filtered off. It is washed with a normal sodium solution and then with water and alcohol. After recrystallization from acetic acid and drying under vacuum, it melts at 183: C.

11

651469

c) Preparation of Vamino-2, nitro-3, N-methylaniline

In 230 ml of concentrated sulfuric acid added with 23 ml of water and previously heated to 90 ° C., 0.0716 mol (23 g) of amino-2 is gradually added over 10 minutes, with stirring. nitro-3, N-methyl, N-tosylaniline. When the addition is complete, the reaction medium is maintained for 5 min at 90 ° C., then it is poured onto crushed ice. The acidic aqueous solution obtained is made alkaline with ammonia to precipitate the expected product. It is wrung, washed with water and recrystallized from 40 ml of alcohol. After drying under vacuum, it melts at 93 C.

Analysis for C7H9N302:

Calculated: C 50.30 H 5.39 N 25.15 0 19.16%

Found: C 50.51 H 5.31 N 25.04 0 19.02%

Preparation example 8:

Preparation of N-ß-hydroxypropylamino-2 nitro-3, methvl-5 aniline hydrochloride

Analysis for C10H15N3O3, HCl:

Calculated: C 45.89 H 6.12 N 16.06 O 18.36 Cl 13.58% Found: C 45.96 H 6.14 N 16.19 O 18.43 Cl 13.76%

5 Preparation example 9:

Preparation of N-ß, y-dihydroxypropylamino-2, nitro-3 hydrochloride. 5-methyl aniline nh-ch0-choh-ch2oh och3

° * nsvà / n0 *

NII-CH2C (iOIÏ-CH3

OCH

o2ny X.

nh,

, HCl o2n \ / x ch.

3

n02

ch.

NH-CH2-CHOH-CH3

NH, - CH, - CHOH - CH,

NH-CH2-CHOH-CH3

OîNX / k / NHj

I Ï

V

nei ch.

a) Preparation of dinitro-2,6 methyl-4 N-ß-hydroxypropylaniline

0.05 mol (10.6 g) of 2,6-dinitro-4-methyl anisole is gradually introduced, with stirring, into 30 ml of 1-amino-2-propanol. The reaction medium is brought to 60 ° C. for 30 min, then it is poured into 120 g of ice water. The expected product precipitates. It is wrung, washed with water and then recrystallized using a hydroalcoholic mixture. After drying under vacuum, it melts at 80 ° C.

Analysis for C10H13N3Os: Calculated: C 47.06 H 5.13 Found: C 47.05 H 5.10

Y 31.34 N 16.47% O 31.44 N 16.36%

, HCl

NH, CH2CHOHCH, OH

ch.

! \ ilî -CH2CHOH -CH2OH

30

K'H- CH2 (JIIUH-CH2UH

, HCl b) Preparation of N-ß-hydroxypropylamino-2 nitro- hydrochloride

3. 5-methyl aniline

0.02 mol (5.10 g) of 2,6-dinitro-4 methyl-N-β-hydroxypropylaniline is dissolved in 40 ml of absolute alcohol containing 0.1 mol (8.6 g) of cyclohexene. 2.5 g of 10% Pd / C are added, then the alcoholic solution is brought to reflux for 10 min. After cooling, the reaction medium is filtered to remove the catalyst. About 20 ml of alcohol are removed in vacuo, then 7 ml of ethanol saturated with hydrochloric gas are added. After cooling to -10 "C, the expected product crystallizes. It is wrung, washed with a little alcohol, then recrystallized using absolute alcohol. After drying under vacuum, the expected hydrochloride melts with decomposition between 145 and 150th C.

a) Preparation of dinitro-2,6 methyl-4 N-ß, y-dihydroxypropyl-35 aniline

0.05 mol (10.6 g) of 2,6-dinitro-4-methyl anisole is dissolved in 50 ml of absolute alcohol. To this solution is gradually added, with stirring, 0.1 mol (9.1 g) of amino-1-propanediol-2,3. The solution is brought to reflux for 314 h. The alcohol is removed in vacuo and 40 40 ml of ice water is added to the residual red oil. The expected product crystallizes. It is wrung out and washed with water. After recrystallization using a hydroalcoholic mixture and drying under vacuum, it melts at 118 ° C.

Analysis for C10H13N3O6:

45 Calculated: C 44.28 H 4.80 N 15.50 0 35.42%

Found: C 44.33 H 4.80 N 15.72 0 35.80%

b) Preparation of N-ß, y-dihydroxypropylamino-2, nitro-3, methyl-5 aniline hydrochloride

50 0.03 mol (8.13 g) of 2,6-dinitro-methyl 4 N-β, γ-dihydroxypropylaniline is dissolved in 60 ml of absolute alcohol containing 12.3 g of cyclohexene. 4 g of 10% Pd / C are added. The alcoholic solution is brought to reflux for 10 min. After cooling, the reaction medium is filtered to remove the catalyst. About 30 ml of alcohol are removed in vacuo, then 8 ml of ethanol saturated with hydrochloric gas are added. After cooling to -10 ° C, the expected product precipitates. The hydrochloride is drained, washed with a little ethyl ether and dried under vacuum. After two recrystallizations from absolute alcohol, the expected product melts with decomposition between 130 60 and 134cC.

Analysis for C10H15N3O4, HCl:

Calculated: C 43.24 H 5.77 N 15.14 0 23.06 Cl 12.79% Found: C 43.18 H 5.82 N 15.30 0 23.10 Cl 12.88%

65

Preparation example 10:

Preparation of N-methylamino-2, nitro-3, methyl-5 aniline

651,469

12

Ki ir H

NH, CH,

nhch.

rhch.

02NV

NO,

OaNV /

V

CH-

NHj

CH.

Analysis for C8H9N304:

Calculated: C 45.50 H 4.27 N 19.91 0 30.33%

Found: C 45.40 H 4.38 N 19.94 0 30.26% b) Preparation of N-methylamino-2, nitro-3, methyl-5 aniline

0.0407 mol (8.6 g) of 2,6-dinitro-4-methyl-N-methyl aniline is dissolved in 45 ml of alcohol containing 0.203 mol (16.7 g) of cyclohexene. 4.3 g of 10% Pd / c are added. The mixture is brought to reflux for 20 min, then the boiling reaction medium is filtered to remove the catalyst. By cooling the filtrate, the expected product crystallizes. It is wrung, washed with a little alcohol and recrystallized from ethanol. After drying under vacuum, it melts at 131 ° C.

Analysis for C8Hj iN302:

Calculated: C 53.04 H 6.08 N 23.20 0 17.68%

Found: C 53.07 H 6.06 N 23.26 0 17.57%

nh-CH2-CH2-N ^

// C2H5

a) Preparation of 2,6-dinitro-methyl-4, N-methylaniline

To 40 ml of a 33% solution of methylamine in ethanol, 0.05 mol (18 g) of 2,6-dinitro-4-methylchlorobenzene is added little by little with stirring. The temperature rises to 50 ° C and the expected derivative precipitates immediately. When the addition is complete, stirring is continued for 5 min, then the 2,6-dinitro-methyl-4, N-methylaniline is filtered off and washed with water, which, after recrystallization from alcohol and drying under vacuum, 132 ° C.

cyclohexene PD / C 10%

c2h5

02N \ / VNH2

T

CH.

a) Preparation of dinitro-2,6 methyl-4, N, N-dielethylaminoethyl-aniline

0.05 mol (10.8 g) of 2,6-dinitro-methyl 4-chlorobenzene in 25 ml of N, N-diethyl-aminoethylamine is added little by little, with stirring, over 10 min, while cooling the reaction medium so as not to exceed 50 ° C. When the addition is complete, stirring is continued for 5 min, then the reaction medium is poured into 150 ml of ice water. The expected product precipitates. It is drained, washed with water and recrystallized from ethanol. After drying under vacuum, it melts at 12 ° C.

Analysis for C13H20N4O4:

Calculated: C 52.70 H 6.76 N 18.92 0 21.62%

Found: C 52.59 H 6.79 N 18.99 0 21.50%

b) Preparation of N ^ -diethylaminoethylamino-2, nitro-3, methyl-5 aniline

0.03 mol (8.52 g) of 2,6-dinitro-methyl, 4, N, N-diethylaminoethylaniline is dissolved in 42 ml of ethanol containing 0.15 mol (12.3 g) of cyclohexene and 4, 3 g of 10% Pd / C. The reaction mixture is brought to reflux for 30 min, then it is filtered while boiling to remove the catalyst. After cooling, 30 ml of hydrochloric ethanol (containing 7 mol of hydrochloric gas per liter) are added to the filtrate. The expected product precipitates in the form of the hydrochloride. The hydrochloride is drained, washed with a little acetone, then dissolved in 30 ml of water. By neutralizing this aqueous solution with ammonia, the N-ß-diethylaminoethylamino-2, nitro-3, methyl-5 aniline is precipitated. This product is filtered, washed with water and then recrystallized from alcohol at 95 ° C. 40 After drying under vacuum, it melts at 45 ° C.

Analysis for C13H22N402:

Calculated: C 58.65 H 8.27 N 21.05 0 12.03%

Found: C 58.75 H 8.29 N 21.03 0 11.92%

Preparation example 11:

Preparation of N-fi-idethylaminoethylamino-2, nitro-3, methyl-5 aniline jïlî-ch -ch2-n nh-

o2n \ y

\

CH.

Preparation example 12:

Preparation of N-ß-hydroxyethylamino-2, nitro-3 aniline nh-ch2-ch oh nh ~ ch2c1i oh

, c2h.

nh-ch2ch2-n c H H2N-CH2CH2OH ° 2N \ y \ / N02 y * 2 5 60

\

H2N — CH2 — CH2 — N oîN \ ^ \ i / no2

c2h5

V

c2h5

nh ~ ch2cii oh

CH.

V

NH

OiNX / k / NH, [

V

a) Preparation of dinitro 2,6-N-fi-hydroxyethylaniline

0.05 mol (10.125 g) of 2,6-dinitro-chlorobenzene in 25 ml of ethanolamine is added little by little, with stirring, while cooling the reaction medium so that the temperature does not exceed 50 C. The reaction medium is poured in 100 ml of ice water. The expected product precipitates. It is wrung, washed with water, recrystallized from ethanol. After drying under vacuum, it melts at 100 ° C.

Analysis for C8H9N305:

Calculated: C 42.29 H 3.96 N 18.50 O 35.24%

Found: C 42.36 H 4.05 N 18.44 0 35.30%

b) Preparation of N-ß-hydroxyethylamino-2, nitro-3 aniline

After adding 0.04 mol (9.1 g) of dinitro-2,6, N-ß-hydroxy-

ethylaniline to 160 ml of absolute ethanol added with 16 ml of ammonia at 22e B, hydrogen sulfide is bubbled for 30 min in this alcoholic solution. The bubbling is stopped, then the reaction medium is brought to reflux for 2 h. The boiling alcoholic solution is filtered to remove the mineral salts, then the filtrate is evaporated to dryness. The red residue obtained is redissolved hot in alcohol. By cooling, the expected product crystallizes. We

13 651469

wring it out, wash it with a little cold alcohol and dry it under vacuum. It melts at 78 ° C.

Analysis for C8H! iN303:

Calculated: C 48.73 H 5.58 N 21.32 0 24.37% 5 Found: C 48.88 H 5.61 N 21.46 O 24.49%

The different trade names used in the examples are explained in more detail below:

Carbopol 934: polymer of acrylic acid of PM 2 to 3 mil-10 lions sold by Goodrich Chemical Company.

Cémulsol NP4: 4 mol nonylphenol of ethylene oxide sold by Rhône-Poulenc.

Cémulsol NP9: 9 mol nonylphenol of ethylene oxide sold by Rhône-Poulenc.

15 Alfol C16.18 (50/50): cetylstearyl alcohol sold by the company Condéa.

Lanette wax E: partially sulfated cetylstearyl alcohol sold by Henkel.

Cémulsol B: ethoxylated castor oil sold by Rhône-Poulenc. 20 Masquol DTPA: sodium salt of diethylenetriamine-pentacetic acid.

Trilon B: sodium salt of ethylenediaminetetracetic acid.

R

Claims (17)

651,469 2 1. Dye composition for keratin fibers, characterized in that it contains at least one dye corresponding to formula (I): nhr, Z nhri (I) in which R, and R2 denote, independently of one another, a hydrogen atom, an alkyl group, a mono- or polyhydroxylated alkyl group, an alkyl group substituted by an alkoxy group, an aminoalkyl group, the amino group of which may optionally be mono- or disubstituted by an alkyl group, the radical R2 can also denote a phenyl group, or phenyl substituted by an alkyl, hydr-oxyl or amino group, Z denotes a hydrogen atom or an alkyl group or their salts cosmetically acceptable. 2. Dye composition for keratin fibers according to claim 1, characterized in that it contains at least one dye of formula (I) in which Z denotes hydrogen or methyl, R2 denotes hydrogen, methyl, ethyl, propyl, butyl, ß -hydroxyethyl, ß-hydroxypropyl, ß.y-dihydroxypropyl, ß-methoxyethyl, N, N-diethylaminoethyl, p-hydroxyphenyl, Rj denotes hydrogen, methyl, ethyl or ß-hydroxyethyl. 3. Composition according to claim 1, characterized in that the dye corresponds to formula (I) in which Z denotes methyl or in which R2 is other than hydrogen. 4. Dye composition according to one of claims 1 to 3, intended for dyeing human hair, characterized in that it contains in a cosmetically acceptable medium at least one compound of formula (I) in proportions of 0.001 to 5% by weight. 5. Dye composition according to one of claims 1 to 4, characterized in that it contains a solvent chosen from water, lower alkanols, polyols, glycols or glycol ethers or their mixtures. 6. Composition according to the eu of claims 1 to 3, characterized in that it contains, in addition to the cosmetic adjuvants chosen from surfactants, thickeners, penetration agents, sequestrants, film formers, tampons, perfumes, basifying or acidifying agents. 7. Composition according to one of claims 1 to 6, characterized in that it has a pH between 3 and 11.5 and preferably between 5 and 11.5. 8. Composition according to one of claims 1 to 4, intended to be used for direct dyeing of the hair, characterized in that it contains, in addition to other direct dyes chosen from azo, anthraquinone dyes, derivatives nitrates of the benzene series other than those of formula (I). 9. Composition according to one of claims 1 to 4, intended for use as a styling lotion, characterized in that it is in the form of an aqueous, alcoholic or hydroalcoholic solution, containing at least one cosmetic resin. 10. Composition according to one of claims 1 to 4, intended to be used for oxidation dyeing, characterized in that it additionally contains at least dye precursors by oxidation. 11. Composition according to claim 10, characterized in that it has a pH of between 7 and 11.5 and that it additionally contains a reducing agent. 12. Process for dyeing keratin fibers, characterized in that a composition according to one of claims 1 to 11 is applied to the fibers, it is left to stand for 5 to 70 min, the fibers are rinsed and dried. 13. A process for dyeing keratin fibers according to claim 12, characterized in that one applies to the fibers 5 washed and rinsed a composition according to claim 9, which is optionally rolled up and dried. 14. A process for dyeing keratin fibers according to claim 12, characterized in that a composition according to one of claims 10 or 11 is applied to the fibers, optionally added with an oxidizing agent which is left to stand for 10 to 50 minutes, rinse, wash with shampoo, rinse again and dry. 15. Nitroorthophenylenediamine derivatives, characterized in that they correspond to the formula: 15 NHR ', 20 O ^ nv / X / NHR-! (II) in which R \ and R'2 denote, independently of each other, a hydrogen atom, an alkyl group, a mono- or polyhydroxy alkyl group, an alkyl group substituted by an alkoxy group, an aminoalkyl group, the group of which amino can optionally be mono- or disubstituted by an alkyl group, the radical R'2 can also denote a phenyl or phenyl group substituted by an alkyl, hydroxyl or amino group, and Z 'denotes a hydrogen atom or an alkyl group under provided that R'j, R'2 and Z 'cannot simultaneously denote hydrogen, when R'2 denotes methyl or phenyl R \ and Z' cannot both denote hydrogen simultaneously, when Z 'denotes methyl at least one groups R'j or R'2 is different from hydrogen, when R'j and R'2 denote methyl Z 'is different from hydrogen, and their cosmetically acceptable salts. 16. Process for the preparation of compounds according to claim 15, characterized in that, when R'j denotes hydrogen, the compounds of formula (III ') are reduced using an alkali sulfite or by transfer of hydrogen from cyclohexene to the compound of formula (III '): NHR'2 (III ') 02n \ y - \ / n02 X, Z ' 17. Process for preparing the compounds according to claim 55, in which R't denotes alkyl or substituted alkyl, characterized in that a benzenesulfonation or a selective paratoluenesulfonation is carried out of the compounds of claim 15, for which R '! denotes H, which is reacted on the aryl sulfonamides obtained with a haloalkane of formula XR'j in la-60 which X denotes halogen and R't has the meaning indicated above, and which the Sulfonamides are hydrolyzed after substitution. As is well known, keratin fibers and in particular human hair are often given a direct color 3 651,469 or additional reflections in the case of oxidation coloring using nitro derivatives of the benzene series. The licensee discovered that nitroorthophenylenediamines could be used, contrary to what might be expected, to give the keratin fibers red shades. This is particularly surprising when it is known that nitro-4-orthophenylenediamine gives rise to yellow coloring. It has found that the hair dyes thus obtained using this class of dyes have good light stability. io These dyes also have the advantage of being little or not selective. Selectivity is, as is well known, an important practical problem in the field of hair dyeing, due to the different sensitization of the hair from root to tip. Indeed, the hairdresser is generally in the presence of a hair of which the sensitization is practically zero for the freshly pushed root, strong for the previously treated parts having undergone coloring, discoloration or a perm, and very strong for the tips who have undergone several of these treatments and who are exposed daily to the action of light and the weather. The licensee discovered that the new class of nitro-3-ortho-phenylenediamines used makes it possible to obtain substantially similar coloring intensities, whether the hair is permed or not. 25 It also found that the dyes used in accordance with the invention were particularly stable in the oxidation dye supports and in particular in an ammoniacal medium in the presence of reducing agents, which makes it possible to combine them with the so-called oxidation dyes to obtain nuances rich in reflections. 30