CH669596A5 - - Google Patents

Description

DESCRIPTION

The present invention relates to new nitro-2, amino-4, hydroxyalkyl-6 anilines, to their process of preparation and to their use in dyeing keratin fibers, in particular human hair.

It is well known that, to give the hair direct coloring or complementary reflections in the case of oxidation coloring, it is possible to use nitro derivatives of the benzene series. The use of nitroparaphenylenediamines has already been recommended, the nitrogen atoms of which are mono- or disubstituted, both in direct dyeing and in oxidation dyeing.

Unfortunately, it has been found, in general, that these nitroparaphenylenediamines have insufficient stability to weathering and washing. The licensee therefore looked for new nitro dyes with better weathering and washing stability, and this is how it discovered the new compounds of formula (I):

X-OH

, SHR,

in which:

X denotes a branched or unbranched alkylene radical containing 2 to 6 carbon atoms, one of these atoms possibly being substituted by one or more hydroxyl radicals;

and R2 denote, independently of one another, a hydrogen atom, an alkyl, mono- or polyhydroxyalkyl or aminoalkyl radical, the amine function of which can be mono- or disubstituted by an alkyl or mono- or polyhydroxyalkyl radical, l the nitrogen atom can also be part of a heterocycle, the alkyl radical having 1 to 4 carbon atoms;

R 'denotes a hydrogen atom or a Ct to C4 alkyl radical.

The present invention therefore relates to the new nitro-2, amino-4, hydroxyalkyl-6 anilines of formula (I) indicated above, as well as their cosmetically acceptable salts.

As preferred X radicals, mention may be made of ethylene, propylene, 1,1-dimethyl ethylene, 1,2-dimethyl ethylene and tri-methyl-1,1,2 ethylene radicals.

As radicals R! and R2 more particularly preferred according to the invention, mention may be made of hydrogen, methyl, ethyl, n-propyl, p-hydroxyethyl, y-hydroxypropyl, ß, y-dihydroxypro-pyl, aminoethyl, P-diethylaminoethyl radicals.

The radicals R 'preferred according to the invention are hydrogen and the methyl radical.

Preferred compounds of formula (I) according to the invention are: - (2,5-diamino, 3-nitro) 2-phenyl-1-ethanol;

- (diamino-2,5, nitro-3) phenyl-1 propanol-2;

- [amino-2, (P-hydroxyethyl) amino-5, nitro-3] phenyl-1 propanol-2,

as well as their salts.

The present invention also relates to a process for the preparation of the compounds of formula (I).

Nitro-2, amino-4, hydroxyalkyl-6 anilines of formula (I)

according to the invention are prepared according to a process which consists in reacting an aqueous ammonia solution with a heterocyclic compound of formula (IV) below, then in carrying out a selective reduction of 2,4-dinitro , hydroxyalkyl-6 aniline of formula (III) obtained, to obtain a nitro-2, amino-4, hydroxyalkyl-6 aniline of formula (II), which is then optionally subjected to a conventional chemical process of alkylation, hydroxyalkylation or aminoal-15 kylation to obtain the final compound of formula (I).

The process diagram is as follows:

©

selective

30 R 'and X having the meaning indicated above.

This process makes it possible to obtain excellent yields of final compound of formula (II) or (I).

The reaction of ammonia with the heterocyclic compound of formula (IV) is carried out at a temperature between 20 and 35 120 ° C., optionally under pressure and optionally in the presence of polar protic solvents such as water, alcohols, glycols or ethers of glycols, or of polar aprotic solvents such as formamide, dimethylformamide, dioxane, tetrahydrofuran.

40 The selective reduction of the compound of formula (III) is carried out by hydrogen transfer from cyclohexene to compound (III), Pd / C being used as catalyst, in the presence of alcohol, water and an acid. mineral such as concentrated hydrochloric acid.

The compounds (II) can also be obtained by selective reduction of the compounds (III), in a polar solvent such as a Cj-Cs alcohol, by the introduction of hydrogen, in the presence of a hydrogen catalyst such as Pd / C and an aqueous solution of a mineral acid such as HCl, H2SO4 or H3PO4, at a temperature between 20 and 90 ° C. This process is described in French patent n ° 1303215.

The compounds of formula (IV) are obtained by nitration of the compounds of formula (V) below:

55

(V)

60 in which X and R 'have the meanings indicated above.

The compounds of formula (V) are known.

Nitration is carried out by adding the compound (V) to fuming nitric acid at a temperature between 30 and 35 ° C according to G. Chatelus, "Ann. Chim. " 4, 505-547 (1949) or by adding the 65 compound (V) to a sulfonitric mixture at a temperature close to 5 ° C, according to Charles D. Hurd, Rostyslaw Dowbenko, "JACS" 80, pp. 4711-14 (1958). The dinitrated compound (IV) is isolated by dilution of the reaction medium with water.

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4

The compounds of formula (IV) in which X denotes the radical ethylene, propylene, dimethyl-1,1 ethylene, dimethyl-1,2 ethylene or trimethyl-1,1,2 ethylene are known.

The conventional alkylation, hydroxyalkylation or aminoalkylation processes used to obtain the final compound of formula (I) from the compound of formula (II) can be, for example, those described in patents FR 2,348,911, 2,497. 662 and 2,492,370 of the licensee or other conventional methods.

The present invention also relates to a dye composition for keratin fibers, in particular for human hair, containing a nitro-2, amino-4, hydroxyalkyl-6 aniline of formula (I) above, as well as a process for coloring keratin fibers, in particular human hair, using said dye composition.

The dye compositions in accordance with the invention contain, in a solvent medium, at least one compound corresponding to formula (I) or one of its cosmetically acceptable salts, and can be used for the direct coloring of keratin fibers or for the oxidation coloration of these fibers, in which case the compounds of formula (I) confer reflections complementary to the basic coloration obtained by oxidative development of oxidation dye precursors.

These components contain the compounds according to the invention in proportions of between 0.001 and 5% by weight and preferably between 0.05 and 2% by weight relative to the total weight of the composition.

The solvent medium is preferably a cosmetic vehicle generally consisting of water, but it is also possible to add,

in the compositions, organic solvents 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, aromatic alcohols such as benzyl alcohol, polyols such as glycerols, glycols or glycol ethers such as 2-butoxyethanol or l 2-ethoxy ethanol, ethylene glycol, propylene glycol, monomethyl ether and monoethyl ether of diethylene glycol as well as analogues and mixtures thereof. 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.

These compositions can contain anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof. 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 compositions can preferably be thickened with compounds chosen from sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethylcelululose, 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 2% 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, dispersing agents, sequestering agents, film-forming agents, buffers and perfumes.

These compositions can be in various forms such as liquid, cream, gel 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, potassium or ammonium carbonate, sodium or potassium hydroxides, alkanolamines such as mono- , di- or triethanolamine, 2-amino-2-methyl-propanol-1, 2-amino-methyl-2-propanediol-1,3, alkylamines such as ethylamine or triethylamine or using d 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 tetraamino-1 , 4,5,8 anthraquinone, indophenols, indoanilines and nitro dyes of the benzene series different from the compounds of formula (I).

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, used in a dyeing process by direct coloring, are applied to the keratin fibers for an exposure time varying from 5 to 50 minutes, then the fibers are rinsed, optionally washed with shampoo, rinsed again and dried.

The compositions according to the invention can also be used in the form of hair styling lotions intended at the same time to give the hair a slight coloration or reflections and to improve the behavior of 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 optionally coiled and then dried.

The cosmetic resins used in the setting lotions can be in particular polyvinylpyrrolidone, copolymers of crotonic acid - vinyl acetate, vinylpyrrolidone-vinyl acetate, maleic anhydride - butyl vinyl ether, maleic anhydride-methyl vinyl ether and any other cationic, anionic, nonionic or amphoteric polymer usually used in this type of composition. These cosmetic resins are included in the compositions of the invention in an amount of 0.5 to 4% by weight, and preferably from 1 to 3% by weight based on the total weight of the composition.

When the compositions according to the invention constitute oxidation dyes involving revelation by an oxidant, 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) and optionally other direct dyes, dye precursors by oxidation.

They may for example contain paraphenylenediamines such as paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-dimethyl-3-methoxy-paraphenylenediamine, N- (ß-methoxyethyl) par N, N-bis- (P-hydroxyethyl) -paraphenylenediamine, N, N- (ethyl, carbamylmethyl) amino-4-aniline, as well as their salts.

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

They may also contain orthoaminophenol.

They can also contain heterocyclic derivatives, for example 2,5-diamino pyridine, 7-amino benzomorpholine.

The compositions according to the invention may contain, in combination with the precursors of colorants by oxidation, couplers well known in the state of the art.

As couplers, there may be mentioned in particular: metadipheols, metaaminophenols and their salts, metaphenylenediamines and their salts, metaacylaminophenols, meta-ureidophenols, metacarbalcoxy aminophenols.

Mention may finally be made, as other couplers which can be used in the compositions of the invention, of a-naphthol, of the couplers pos-

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sedating an active methylene group such as diketo compounds and pyrazolones and heterocyclic couplers derived from pyridine and benzomorpholine.

These compositions contain, in addition to dye precursors by oxidation, reducing agents present in proportions of between 0.05 and 3% 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. The pH of these oxidation dyeing compositions is preferably between 7 and 11.5 and is adjusted using alkalinizing agents defined above.

The process for dyeing keratin fibers, in particular human hair, using revelation with an oxidant, consists in applying to the hair the dye composition comprising both a dye according to the invention and the dye precursors. The development of the coloration can then be carried out slowly in the presence of oxygen from the air, but preferably a chemical developing system is used which is most often chosen from hydrogen peroxide, urea peroxide and parsley. 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 minutes, preferably 15 to 30 minutes, 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.

Preparation example 1

Preparation of (diamino-2,5rnitro-3'fphenyl-2 ethanol-1

of 64 ml of cyclohexene, 0.141 mol (32 g) of (2-amino, 3,5-dinitro) 2-phenyl ethanol-1 is added. After 13 hours of heating at reflux, the reaction medium is filtered hot to remove the catalyst. The filtrate is evaporated to dryness under vacuum and the dry extract, after being washed with absolute ethanol, is dissolved hot in water. 15 ml of 20% ammonia are added. By cooling, a red precipitate of the expected product is obtained which, after spinning, is recrystallized from methylcellosolve. After drying, the product melts at 190 ° C.

Molecular mass calculated for C8HnN303: 197.

io Molecular mass found by potentiometric determination in acetic acid with perchloric acid: 199.5.

Analysis of the product obtained gives the following results:

Analysis for CgHjjNjOs: Calculated: C 48.72 H 5.62

Found: C48.8

H 5.67

N 21.31 N 21.33

O 24.34% O 24.60%

Preparation example 2

Preparation of (2,5-diamino, 3-nitro) 1-phenyl-2-propanol

° 2V ^

NH3 / CH3OCH2CH2OH

choech,

kb,

1 "step

Preparation of (2-amino, 3,5-dinitro) 2-phenyl ethanol-1

Is suspended in 350 ml of 20% ammonia and 220 ml of formamide 0.17 mole (35.7 g) of 2,3-dihydro, 5,7-dinitro benzofuran prepared according to Chatelus, "Ann. Chim. " [12], 4, 505-547 (1949).

After 8 hours of heating at 110 ° C., 100 ml of 20% ammonia are added. Heating is maintained for 4 hours. By cooling the reaction medium, the expected product precipitates.

After spinning, washing with ice-cold water until neutral and drying under vacuum, 0.13 mol (30.3 g) of a product melting at 151 ° C. is obtained, which is recrystallized from dioxane.

Analysis of the product gives the following results:

Analysis for C8H9N3Os:

Calculated: C 42.29 H 3.99 N 18.50 0 35.21% Found: C 42.24 H 3.91 N 18.60 0 35.14%

¥ stage

Preparation of (diamino-2,5, nitro-3) phenyl-2 ethanol-1

To a suspension of 15.7 g of Pd / C at 10% in 290 ml of absolute ethanol with the addition of 35 ml of concentrated hydrochloric acid and

Preparation of (2-amino, 3,5-dinitro) 1-phenyl-2-propanol

35 Is suspended in 1.1 liters of 20% ammonia and 600 ml of methylcellosolve 0.39 mole (88 g) of 2,3-dihydro, dinitro-5,7, 2-methyl benzofuran prepared according to "JACS »80, pp. 4711-14 (1958). After 18 hours of heating at 70 ° C., the reaction medium is cooled. The precipitate formed is drained which, after re-pasting in water until neutral, then drying under vacuum, is recrystallized from 170 ml of dioxane. After drying under vacuum, 0.30 mol (72 g) of the expected product is obtained; it melts at 177 ° C.

The analysis gives the following results:

Analysis for CqHj! N305:

Calculated: C 44.81 H 4.60 N 17.42 0 33.17% Found: C 44.87 H 4.62 N 17.45 0 33.08%

? step

50 Preparation of (2,5-diamino, 3-nitro) 1-phenyl-2-propanol

To a suspension of 5.6 g of Pd / C at 10% in 100 ml of absolute ethanol supplemented with 12.5 ml of concentrated hydrochloric acid and 23 ml of cyclohexene, 0.05 mol is added (12.05 g) (2-amino, 3,5-dinitro) phenyl-1 propanol-2. After 3 hours of heating at 55 reflux, the reaction medium is filtered hot to remove the catalyst. The filtrate is evaporated to dryness, the dry extract is re-pasted in an ethanol / ethyl ether mixture, then dissolved hot in the minimum amount of water. 15 ml of 20% ammonia are added in order to displace the hydrochloride. The expected product precipitates. After spinning, 60 washing with water and recrystallization from ethanol at 96 °, it melts at 168 ° C. Molecular mass calculated for C9H13N303: 211.

Molecular mass found by potentiometric determination in acetic acid with perchloric acid: 210.

Analysis of the product obtained gives the following results:

6S Analysis for C9Hi3N303:

Calculated: C 51.17 H 6.20 N 19.90 0 22.73% Found: C 51.31 H 6.21 N 20.03 O 22.66%

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Preparation example 3

Preparation of [amino-2, (ß-hydroxyethyl) amino-5, nitro-3] phenyl-1 propanol-2

.C ^ CHOEC ^ j Cl (CE2) 2OCCNH_

cicooch2ch2ci

U2ceoece3

EOCH-CH-JTH

K2co,

, ch2œoech3

KCL

CH3ONa / CH3OH

NO.

1 "step

Preparation of [(amino-4, ß-hydroxypropyl-5, nitro-3) phenyl] ß-chloroethyl carbonate

0.07 mol (14.8 g) of (2,5-diamino, 3-nitro-3) phenyl-1-propanol-2 obtained in Preparation Example 2 is dissolved in 59 ml of dioxane supplemented with 22 ml of water . 0.0385 mole (5.3 g) of potassium carbonate is added. The temperature is raised to 90 ° C., then 0.077 mol (11 g) of β-chloretyl chloroformate is gradually introduced, with stirring. When the addition is complete, the reaction mixture is poured onto 400 g of a water / ice mixture. The expected product precipitates; after draining and drying under vacuum, 21.8 g of the expected product are obtained. It melts at 115 ° C.

? step

Preparation of N - [(amino-4, ß-hydroxypropyl-5, nitro-3) phenyl] oxazolidone

0.056 mol (17.8 g) of P-chloroethyl [(amino-4, ß-hydroxypropyl-5, nitro-3) phenyl] carbamate is suspended in 107 ml of 96 ° alcohol. 12 ml of a 30% sodium methylate solution in methanol are poured in dropwise while maintaining the temperature at 10 ° C. After wringing and re-pasting in water, 0.041 mol (11.6 g) of the expected product is obtained.

3rd stage

Preparation of [amino-2, (fi-hydroxyethyl) amino-5, nitro-3] phenyl-1 propanol-2

0.041 mol (11.5 g) of N - [(amino-4, β-hydroxypropyl-5, nitro-3) phenyl] oxazolidone are introduced into 46 ml of 96 ° alcohol. The temperature is raised to 85 ° C. and 8.2 ml of 10N sodium hydroxide are poured in dropwise. Heating is maintained 15 minutes after the end of the casting. After filtration, the filtrate is evaporated to dryness, then the residue is taken up in 40 ml of water. The expected product crystallizes; after recrystallization of the water, it melts at 130 ° C.

Molecular mass calculated for CI1H17N304: 255.

Molecular mass found by potentiometric determination in acetic acid with perchloric acid: 256.

Analysis of the product obtained gives the following results:

Analysis for CuH17N304:

Calculated: C 51.75 H 6.71 N 16.46 0 25.07% Found: C 51.80 H 6.70 N 16.62 0 25.18%

Example 1

We prepare the following dye composition

(2,5-Diamino, 3-nitro) 2-phenyl-1-ethanol 0.54 g

Butoxy-2 ethanol 15 g

Cellosize WP 03 2 g

Dimethylhydroxyethylammonium alkyl (tallow) chloride 2 g

Monoethanolamine in 20% aqueous solution 1 g

Water qs 100 g pH = 9.8

This mixture, applied 15 minutes at 30 ° C on hair, gives them, after shampooing and rinsing, a coloring:

7.5 R 5/10 on hair bleached white,

7.5 R 5.5 / 6 on naturally white hair at 90%,

these colors being expressed according to the Munsell notation.

Example 2

The following dye composition is prepared:

(2,5-Diamino, 3-nitro) 1-phenyl-2-propanol 0.3 g

Butoxy-2 ethanol 10 g

96 ° alcohol 5 g

35 Cellosize WP 03 2 g

Ammonium lauryl sulfate - 5 g

Water qs Ï0Ô g pH = 6.9

This mixture, applied 20 minutes at 28 ° C to hair, 40 gives them, after shampooing and rinsing, a coloring: 8 R 5/10 on hair bleached with white,

7.5 R 5.5 / 6 on naturally white hair at 90%, these colors being expressed according to the Munsell notation.

45 Example 3

The following dye composition is prepared:

[Amino-2, (ß-hydroxyethyl) amino-5, nitro-3]

1-phenyl-2-propanol 0.7 g

50 96 ° alcohol 10 g

Alfol C] 6/18 8 g

Lanette wax E 0.5 g

Cemulsol B 1 g

Oleic diethanolamide 1.5 g 55 5% ammonia qs pH = 9.9

Water qs 100 g

This mixture, applied 10 minutes at 28 ° C on hair, gives them, after shampooing and rinsing, a coloring:

7.5 RP 4/9 on hair bleached white,

60 7.5 RP 5.5 / 4 on 90% naturally white hair,

these colors being expressed according to the Munsell notation.

Example 4

65 The following dye composition is prepared:

(2,5-Diamino, 3-nitro) 1-phenyl-2-propanol 0.16 g

Amino-2, nitro-3 toluene 0.095 g

Nitro-3, y-hydroxypropylamino-4 aniline 0.12 g

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Tetraamino-1,4,5,8 anthraquinone (blue sapphire cibacète microdispersed) 0.12 g

Lauramide 1.5 g

Lauric acid 1 g

Cellosize WP 03 5 g

Monoethanolamine 2 g

Water qs 100 g pH = 9.5

This mixture, applied 20 minutes at 28 ° C to naturally white hair at 90%, gives them, after shampooing and rinsing, a coppery blond coloring.

Example 5

The following dye composition is prepared:

(2,5-Diamino-3-nitro) 2-phenyl-1-ethanol 0.2 g

Amino-2, 3-nitro phenol 0.15 g Nitro-3 hydrobromide, 4-methylamino,

N- (p-aminoethyl) aniline 0.08 g

96 ° alcohol 10 g

Lauramide 1.5 g

Lauric acid 1 g

Cellosize WP 03 5 g

Monoethanolamine 2 g

Water qs 100 g pH = 9.7

This mixture, applied for 25 minutes at 28 ° C on hair bleached with white, gives them, after shampooing and rinsing, a red copper coloring.

Example 6

The following dye composition is prepared:

[Amino-2, nitro-3 (P-hydroxyethyl) amino-5]

1-phenyl-2-propanol 0.36 g

Nitro-3, 4-amino phenol 0.13 g P-hydroxyethylamino-2, (di-p-hydroxyethylamino-4

amlmo) -5 benzòquinone-1,4 -, »0.17 g

96 ° alcohol 20 g

Cellosize WP 03 2 g Alkyl chloride (tallow) dimethylhydroxyethyl-

ammonium 2 g

0.2% triethanolamine 0.2 g

Water qs 100 g pH = 7.7

This mixture, applied 20 minutes at 28 ° C to naturally white hair at 90%, gives them, after shampooing and rinsing, a coppery blond coloring.

Example 7

(2,5-Diamino, 3-nitro) 1-phenyl-2-propanol 0.7 g [Amino-2, (P-hydroxyethyl) amino-5, nitro-3]

1-phenyl-2-propanol 0.06 g

2,5-diamino dihydrochloride pyridine 0.05 g

Paraaminophenol 0.08 g a-naphthol 0.035 g

Hydroxy-7 benzomorpholine 0.07 g (2,4-diamino) phenoxy-1 dihydrochloride

propanediol-2,3 0,04 g N-P-methoxyethyl di-hydrochloride

paraphenylenediamine 0.04 g

Polyglycerolated oleic alcohol with 2 moles of glycerol 4.5 g

Polyglycerolated oleic alcohol with 4 moles of glycerol 4.5 g

Ethomeen TO 12 4.5 g

Comperlan KD 9 g

Propylene glycol 4 g

Butoxy-2 ethanol 8 g

Ethanol at 96 ° 6 g

Masquol DTPA 2 g

Hydroquinone 0.15 g

Sodium bisulfite solution at 35 ° B 1.3 g

Ammonia at 22 ° B 10 g

Water qs 100 g pH = 10.5

At the time of use, 110 g of hydrogen peroxide are added to 20 volumes.

The mixture, applied 20 minutes at 28 ° C to naturally white hair at 90%, gives them, after shampooing and rinsing, an ash blonde coloring.

Example 8

The following dye mixture is prepared:

[Amino-2, (P-hydroxyethyl) amino-5, nitro-3]

phenyl-1 propanol-2

0.1g

[(P-hydroxyethyl) amino-2, dinitro-3,5]

phenyl-2 ethanol-1

0.08 g

2-methyl resorcin

0.06 g

Paraphenylenediamine

0.05 g

2,4-diamino dihydrochloride phenoxyethanol

0.03 g

Cemulsol NP 4

21g

Cemulsol NP 9

24 g

Oleic acid

4g

Butoxy-2 ethanol

3g

Ethanol at 96 °

10g

Masquol DTPA

2.5g

Sodium bisulfite solution at 35 ° B

1 g

Ammonia at 22 ° B

10g

Water qs

100 g pH = 10.6

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

The mixture, applied 30 minutes at 28 ° C to bleached hair, gives them, after shampooing and rinsing, a bluish gray coloring.

Example 9;

The following dye mixture is prepared:

(2,5-Diamino, 3-nitro) 2-phenyl ethanol-1

0.08 g

(P-hydroxyethylamino-2, dinitro-3,5)

phenyl-2 ethanol-1

0.07 g

Paraphenylenediamine

0.06 g

Resorcin

0.035 g

Acetamido-5, 2-methyl phenol

0.09 g

Phenyl-1, methyl-3, pyrazolone-5

0.065 g

Carbopol 934

3g

96% alcohol

U g

Butoxy-2 ethanol

5g

Alkyl chloride (tallow) dimethylhydroxyethyl-

ammonium

2g

Trilon B

0.2g

Ammonia at 22 ° B

10g

Sodium bisulfite at 35 ° B

1g

Water qs

100 g pH = 10.2

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

The mixture, applied 20 minutes at 28 ° C to naturally white hair at 90%, gives them, after shampooing and rinsing, a dark pinkish pink coloring.

Example 10

The following dye mixture is prepared:

[Amino-2, (P-hydroxyethyl) amino-5, nitro-3]

1-phenyl-2-propanol 0.08 g

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Paraaminophenol

0.09 g

1,4-diamino dihydrochloride, 2,6-dimethyl dihydrochloride

benzene

0.04 g

Resorcin

0.06 g

[Amino-2-hydrochloride, (P-hydroxyethyl)

4-amino] phenoxyethanol

0.05 g

Cellosize WP 03

2g

Ammonium lauryl sulfate

5g

Butoxy-2 ethanol

15g

96% alcohol

5g

Ammonia at 22 ° B

10g

Ammonium thiolactate

0.8 g

Water qs

100 g pH = 10.1

At the time of use, 120 g of hydrogen peroxide are added to 20 volumes.

The mixture, applied 40 minutes at 30 ° C to naturally white hair at 90%, gives them, after shampooing and rinsing, a pearly light gray coloring.

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

Alfol C16 / 18: Cetylstearyl alcohol, sold by the company Condéa. Lanette wax E: Partially sulfated cetylstearyl alcohol, 5 sold by Henkel.

Cemulsol B: Ethoxylated castor oil, sold by Rhône-Poulenc. Cellosize WP 03: Hydroxyethylcellulose, sold by Union Carbide. Lauramide: Monoethanolamide of lauric acid, sold by Witco. Ethomeen TO 12: Oleylamine oxyethylenated with 12 moles of ethylene oxide, sold by Armak.

Comprelan KD: Coconut fatty acid diethanolamide, sold by Henkel.

Masquol DTPA: Pentasodium salt of diethylenetriaminepen-tacetic acid, sold by Protex.

15 Cemulsol NP 4: Nonylphenol oxyethylenated with 4 moles of ethylene oxide, sold by Rhône-Poulenc.

Cemulsol NP 9: Nonylphenol oxyethylenated with 9 moles of ethylene oxide, sold by Rhône-Poulenc.

Carbopol 934: Polymer of acrylic acid with PM 2 to 3 million, sold by Goodrich Chemical Company.

Trilon B: Ethylenediaminetetracetic acid.

r

Claims (19)

669,596 1. Nitro-2, amino-4, hydroxyalkyl-6 aniline of formula (I) below: r ' x-oe nbr, (I) in which: X denotes a branched or unbranched alkylene radical, comprising 2 to 6 carbon atoms, which may be optionally substituted by one or more hydroxyl radicals; R 1 and R 2 denote, independently of one another, a hydrogen atom, an alkyl, mono- or polyhydroxyalkyl or aminoalkyl radical, the amine function of which can be mono- or disubstituted by an alkyl or mono- or polyhydroxyalkyl radical, the nitrogen atom can also be part of a heterocycle, the alkyl radical containing 1 to 4 carbon atoms, and R 'denotes a hydrogen atom or a C1 to C6 alkyl radical C4, and the cosmetically acceptable salts of this compound. 2. Compound according to Claim 1, characterized in that X denotes an ethylene, propylene, 1,1-dimethyl ethylene, di-methyl-1,2 ethylene or trimethyl-1,1,2 ethylene radical, Rt and R2 denote , independently of one another, a hydrogen atom, a methyl, ethyl, n-propyl, ß-hydroxyethyl, 7-hydroxypropyl, ß, y-dihydroxypropyl, aminoethyl or p-diethylaminoethyl radical, and R 'denotes a hydrogen atom or a methyl radical. 2 3 669,596 fibers a composition according to one of claims 7 to 12, leave it on for 5 to 50 minutes, rinse, wash with shampoo, rinse again and dry. 3. Compound according to claim I or 2, characterized in that it is chosen from the group comprising: (2,5-diamino, 3-nitro) 2-phenyl ethanol-1, (2,5-diamino , 3-nitro) phenyl-1 propanol-2, and F [amino-2, (P-hydroxyethyl) amino-5, nitro-3] phenyl-1 propanol-2, and the salts of these compounds. 4. Process for the preparation of a nitro-2, amino-4, hydroxyalkyl-6 aniline of formula (I) according to claim 1 in which Rt and R2 represent hydrogen, characterized in that a solution is reacted aqueous ammonia on a heterocyclic compound of formula: r " (IV) in which R ′ and X have the meanings indicated in claim 1, at a temperature between 20 and 120 ° C, to obtain a 2,4-dinitro-6, 6-hydroxyalkyl aniline of formula: 02K. x-oe which R 1 and R 2 denote, independently of one another, an alkyl, mono- or polyhydroxyalkyl or aminoalkyl radical the amine function of which can be mono- or disubstituted by an alkyl or mono- or polyhydroxyalkyl radical, the nitrogen atom can also be part of a heterocycle, the alkyl radical containing 1 to 4 carbon atoms, or one of the symbols Rj and R2 represents hydrogen and the other is defined as indicated above, characterized by the fact that an aqueous ammonia solution is reacted with a compound of formula (IV) under the conditions defined in claim 4, then the 2,4-dinitro-2,4-hyxdroxyalkyl-6 aniline of formula ( III) thus obtained in the treatment defined in claim 4 to obtain the compound of formula: x-oh (III) in which R ′ and X have the meanings indicated above, then a selective reduction of the compound of formula (III) is carried out by hydrogen transfer from cyclohexene to the compound of formula (III), using Pd / C as catalyst, in the presence of alcohol, water and a mineral acid, or by the introduction of hydrogen to a mixture of dinitrated compound (III), a polar solvent, a hydrogenation catalyst and an aqueous solution of a mineral acid at a temperature between 20 and 90 ° C. 5. Process for the preparation of a nitro-2, amino-4, hydroxyalkyl-6 aniline of formula (I) according to claim 1 in (II) in which R ′ is defined as indicated above, then an alkylation, a hydroxyalkylation or an aminoalkylation of the compound of formula (II) is carried out. 6. Method according to claim 4 or 5, characterized in that The treatment of the compound of formula (TV) is carried out in the presence of polar protic solvents or polar aprotic solvents. 7. Dye composition for keratin fibers, in particular for human hair, characterized in that it contains, in 30 a solvent medium, at least one compound according to one of claims 1 to 3. 8. Composition according to Claim 7, characterized in that it contains 0.001 to 5% by weight, and preferably 0.05 to 2% by weight, relative to the total weight of the composition, of at least one 35 compound of formula (I) according to one of claims 1 to 3. 9. Composition according to claim 7 or 8, characterized in that it has a pH between 3 and 11.5, and preferably between 5 and 11.5. 10. Composition according to one of claims 7 to 9, character- 40 due to the fact that the solvents are chosen from water, lower alkanols, aromatic alcohols, polyols, glycols or glycol ethers and their mixtures. 11. Composition according to one of claims 7 to 10, characterized in that it also contains cosmetic adjuvants 45 chosen from surfactants, anionic, cationic, nonionic, amphoteric or mixtures thereof, thickeners, dispersing agents, penetrating agents, sequestrants, film-forming agents, buffers, perfumes, basifying agents or acidifiers. 50 12. Composition according to one of claims 7 to 11, intended to be used for the direct dyeing of human hair, characterized in that it contains, in addition, other direct dyes chosen from azo dyes, dyes anthraquinones, indophenols, indoanilines and nitro derivatives of 55 the benzene series other than those of formula (I). 13. Composition according to one of claims 7 to 11, intended to be used as a layering lotion, characterized in that it is in the form of an aqueous, alcoholic or hydroalcoholic solution, containing at least one resin cosmetic. 60 14. Composition according to one of claims 7 to 11, intended to be used for oxidation dyeing, characterized in that it also contains at least one dye precursor by oxidation. 15. Composition according to claim 14, characterized by the 65 means that it has a pH between 7 and 11.5 and that it additionally contains a reducing agent. 16. A process for dyeing keratin fibers, in particular human hair, characterized in that one applies to the 17. A process for dyeing keratin fibers, in particular human hair, characterized in that a composition according to claim 13 is applied to the washed and rinsed fibers, it is rolled up and dried. 18. A process for dyeing keratin fibers, in particular human hair, characterized in that a composition according to claims 14 and 15 is applied to the fibers, it is left to stand for 10 to 50 minutes, it is rinsed, washed with shampoo, rinse again and dry. 19. The method of claim 18, characterized in that an oxidizing agent is added to the composition.