CH669595A5 - - Google Patents

Description

DESCRIPTION

The present invention relates to new amino-2, nitro-4, hydroxyalkyl-6 anilines, to their preparation process, 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 nitroorthophénylènediami-nes such as more particularly amino-2, nitro-4, alkyl-6 anilines has already been recommended in both direct dyeing and oxidation dyeing.

However, in general, insufficient stability to light and to washing of these dyes has been found. The licensee therefore sought new dyes with better light and washing stability, and this is how it discovered the new compounds of formula (I):

NHR,

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 each other, 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 having 1 to 4 carbon atoms;

R 'denotes a hydrogen atom or an alkyl radical in Q to

Q.

The present invention therefore relates to the new amino-2, nitro-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.

Preferred radicals R ′ according to the invention are hydrogen and the methyl radical.

Preferred compounds of formula (I) according to the invention are:

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

- [amino-3, P-hydroxyethylamino-2, nitro-5] phenyl-2 ethanol-1;

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

- (3-amino, 2-methylamino, 5-nitro) 1-phenyl-2-propanol,

as well as their salts.

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

Amino-2, nitro-4, hydroxyalkyl-6 anilines of formula (I)

according to the invention are prepared by a process which consists in reacting an aqueous ammonia solution or a primary aliphatic amine R1NH2, in which Rj has the meaning indicated above, on a heterocyclic compound of formula (IV) below , then to carry out a selective reduction of the 2,4-dinitro, 6-hydroxyalkyl-6 aniline of formula (III) obtained, to obtain a 2-amino, 4-nitro, 6-hydroxyalkyl aniline of formula (II), which then optionally subjected to a conventional chemical process of alkylation, hydroxyalkylation or aminoalkylation to obtain the final compound of formula (I).

The process diagram is as follows:

R '

S-OE

+ r, nh2

30

(IV)

Selective reduction n ° 2

(iii)

r '

1

, -x-oe

serj ^

t nh2

(ii)

40

(i)

r ', X and ri having the meaning indicated above.

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

The reaction of the ammonia or of the primary amine on the heterocyclic compound of formula (IV) is optionally carried out under pressure, at a temperature of between 20 and 120 ° C., in the optional presence of polar protic solvents such as l water, alcohols, glycols or ethers of glycols, or polar aprotics such as formamide, dimethylformamide, dioxane, tetrahydro-furan.

n / a The selective reduction of the compound of formula (III) is carried out either by a hydroalcoholic solution of sodium sulfide in the presence of sulfur at a temperature between 10 and 70 ° C, or by hydrogen sulfide in the presence of ammonia according to M. Kamel, MI Ali and MM Kamel, "Tetrahedron" 1966, vol. 22, p. 3353, or also 55 by hydrogen transfer from cyclohexene to compound (III) in the presence of Pd / C, in lower Cj-Q alcohols, at a temperature between 15 ° C and boiling, by analogy with Ian D. Entwistle, Robert AW Johnstene and Jeffery Povall [“JCS Per-kin I "(1975), p. 1300],

6o The compounds of formula (IV) are obtained by nitration of the compounds of formula (V) below:

R '

(V)

in which X and R 'have the meanings indicated above, which are known compounds. Nitration is carried out by adding the

669,595

4

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

The compounds of formula (IV) in which X denotes the radical ethylene, propylene, dimethyl-1,1 ethylene, dimethyl-1,2 ethylene and 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, and more particularly for human hair, containing a amino-2, nitro-4, hydroxyalkyl-6 aniline of formula (I) above, as well as a process for coloring of 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 compositions 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 glycerol, 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, hydroxyethylcel-lulose, hydroxypropylmethylcellulose, carboxymethylcellulose and various polymers having thickening 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 the proportions of between 0.5 and 10% by weight and in particular between 05 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- , io di- or triethanolamine, 2-amino-2-methyl-propanol-1, 2-amino-2-methyl-propanediol-1,3, 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 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 light coloration or reflections 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 optionally coiled and then dried.

The cosmetic resins used in the setting lotions can be in particular polyvinylpyrrolidone, copolymers 40 crotonic acid - vinyl acetate, vinylpyrrolidone - vinyl acetate, maleic anhydride - butylvinyl ether, maleic anhydride - methyl vinyl ether as well as any other cationic, anionic, nonionic or amphoteric polymer usually used in this type of composition. These cosmetic resins fall into the com-45 positions 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 implying revelation by an oxidizing agent, 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. 55 They may contain, for example, para-phenylenediamines such as para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-dimethyl-3-methoxy-para-phenylenediamine, N- (ß-methoxyethyl) , N, N-bis- (p-hydroxyethyl) 60 paraphenylenediamine, N, N- (ethyl, carbamylmethyl) 4-amino aniline, as well as their salts.

They can also contain paraaminophenols, for example paraaminophenol, N-methylparaaminophenol, 2-chloro-4 amino-phenol, 3-chloro-4 amino phenol, methyl-2 65 amino-4 phenol, and their salts.

They may also contain orthoaminophenol.

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

5

669,595

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, mention may be made in particular of metadiphenols, metaaminophenols and their salts, metaphenylenediamines and their salts, metaacylaminophenols, meta-ureidophenols, metacarbaleoxyaminophenols.

Finally, mention may be made, as other couplers which can be used in the compositions of the invention, of a-naphthol, of couplers having an active methylene group such as diketonic compounds and pyrazolones and of 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 by 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 , we rinse them again and dry.

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

Preparation example 1

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

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, "An. 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 C8H9N305:

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% T step

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

To a suspension of 0.119 mole (27 g) of (amino-2, dinitro-3,5) phenyl-2 ethanol-1 in 67.5 ml of isopropanol supplemented with an equal volume of water, drop is added drop, at 60-65 ° C, a solution of 38.4 g of sodium sulfide nonahydrate and 5.4 g of sulfur in 10 ml of water. Heating is maintained 20 minutes after the end of the addition. By cooling, a precipitate of the expected product is obtained which is drained, re-paste in water, then recrystallized from alcohol at 96 °. It melts at 172 ° C.

Molecular mass calculated for CgHuNjOj: 197.

Molecular mass found by potentiometric determination in acetic acid with perchloric acid: 202.

Analysis of the product obtained gives the following results:

30

N 21.31 N 21.40

O 24.34% O 24.30%

Analysis for C8Hj iN303:

Calculated: C 48.72 H 5.62 Found: C 48.84 H 5.71 Preparation example 2

Preparation of [3-amino, 2-hydroxyethylamino-2, 5-nitro] 2-phenyl ethanol-1

KHCH2CH20H

NHCH2CH20H

1 "step

45 Preparation of (fi-hydroxyethylamino-2, dinitro-3,5) phenyl-2 ethanol-1

0.29 mol (60.9 g) of 2,3-dihydro-5,7-dinitro-5,7 benzofuran is added at room temperature to 122 ml of 2-amino ethanol. After the end of the addition, the reaction medium is brought to 15 ° C. for 15 minutes.

500 ml of water are added; after cooling, the expected product is drained which, after re-pasting in water and recrystallization from 75 ml of ethanol at 96 °, melts at 115 ° C.

The analysis gives the following results:

55 Analysis for C10H13N3O6:

Calculated: C 44.28 H 4.83 N 15.49 0 35.39% Found: C 44.38 H 4.74 N 15.48 0 35.60%

2nd stage

60

Preparation of [3-amino, 2-hydroxyethylamino-2, 5-nitro] 2-phenyl ethanol-1

After adding 0.14 mole (38 g) of (P-hydroxyethylamino-2, dinitro-3,5) phenyl-2 ethanol-1 to 530 ml of absolute alcohol added 65 of 56 ml of 20% ammonia, hydrogen sulfide is bubbled for 2 hours in this alcoholic solution; the temperature rises to 27 ° C. The bubbling is then stopped. The reaction medium is brought to reflux for 4 hours, then it is abandoned.

669595

6

48 hours at room temperature. After concentrating the alcoholic solution at half, the mineral salts are filtered. The filtrate is then evaporated to dryness. The dry residue is re-pasted in isopropanol. After recrystallization in order to remove a resin, the product melts at 121 ° C.

Molecular mass calculated for C10H15N3O4: 241.

Molecular mass found by potentiometric determination in acetic acid with perchloric acid: 247.

Analysis of the product obtained gives the following results:

Analysis for C10H15N3O4 ,:

Calculated: C 49.78 H 6.27 N 17.42 O 26.53% Found: C 49.87 H 6.27 N 17.38 O 26.25%

Preparation example 3

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

NH3 / CH3OCH2CH2OH

CHjCEOE ^

Reduction

CH ^ CHOHCH ^

Preparation example 4

Preparation of monohydrochloride (3-amino, 2-aminoamino, 5-nitro) 1-phenyl-2-propanol

CH3NH2 / EtOH

.C ^ CHOECHj

'NHCH,

EC1

1 "step

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

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 CpH ^ Î ^ Os:

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%

2nd stage

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

To a suspension of 0.1 mole (24.1 g) of (amino-2, dinitro-3,5) phenyl-1 propanol-2 in 60 ml of isopropanol added with an equal volume of water, add dropwise at 60 ° C a solution of 33.6 g of sodium sulfide nonahydrate and 4.8 g of sulfur in 9 ml of water.

Heating is maintained 20 minutes after the end of the addition. By cooling, the expected product is obtained which is drained, xéempâtée in water, and recrystallized from alcohol at 96 °. It melts at 174 ° C.

Molecular mass calculated for C9H13N303: 211.

Molecular mass found by potentiometric determination in acetic acid with perchloric acid: 216.

Analysis of the product obtained gives the following results:

Analysis for C9H13N303:

Calculated: C 51.17 H 6.20 N 19.90 0 22.73% Found: C 51.09 H 6.19 N 20.13 O 22.57%

the e stage

Preparation of (methylamino-2, dinitro-3,5) phenyl-1 propanol-2 Is suspended in 100 ml of a solution of methyl-amine at 33% in ethanol 0.056 mol (12.5 g) 2,3-dihydro, 5,7 dinitro, 2-methyl benzofuran. After 10 hours of stirring at room temperature in a stoppered Erienmeyer, the reaction medium is brought to reflux of the alcohol for 30 minutes. After cooling, the expected product precipitates. It is drained, washed with alcohol and then recrystallized from 50 ml of ethanol at 96 °. After drying, 0.047 mol (12 g) of a product melting at 132 ° C. is obtained.

The analysis gives the following results:

Analysis for CioH13N305:

30 Calculated: C 47.06 H 5.13 N 16.47 0 31.34% Found: C 47.11 H 5.03 N 16.52 O 31.25%

? step

Preparation of (amino-3, methylamino-2, 35-nitro-5) monohydrochloride 1-phenyl-propanol-2

After adding 0.027 mole (6.88 g) of (methylamino-2, dinitro-3,5) phenyl-1 propanol-2 to 100 ml of absolute ethano supplemented with 10.8 ml of 20% ammonia, bubbled hydrogen sulfide for 2 Vi hours. After 1 hour, the temperature 40 rises to 35 ° C then falls again. After concentrating at half the alcoholic solution, the mineral salts are filtered. The filtrate is evaporated to dryness; the dry extract in oily form is taken up in a solution of hydrochloric acid in absolute ethanol. By dilution with ethyl ether, the monohydrochloride of the expected product is obtained which is recrystallized from a hydroalcoholic mixture.

Molecular mass calculated for C10HlsN3O3Cl: 261.5.

Molecular mass found by potentiometric determination in water with sodium hydroxide: 264.

Analysis of the product obtained gives the following results:

50

Analysis for Ci0H16N3O3Cl:

Calculated: C 45.89 H 6.12 N 16.06 018.35 Cl 13.57% Found: C 46.00 H 6.13 N 16.21 0 18.38 Cl 13.64%

55 Example 1

The following dye composition is prepared:

(2,3-Diamino, 5-nitro) 2-phenyl-1-ethanol 0.15 g

Propylene glycol 10 g

60 Cemulsol NP 4 12 g

CemulsolNP9 15 g

Polyglycerolated oleic alcohol with 2 moles of glycerol 1.5 g

Polyglycerolated oleic alcohol with 4 moles of glycerol 1.5 g

Monoethanolamine in 20% solution in water 1.5 g

65 Water qs 100 g pH = 10

This mixture, applied 20 minutes at 28 ° C to hair, gives them, after shampooing and rinsing, a coloring:

7

669,595

10 YR 7.5 / 8 on hair bleached white,

5 Y 8/6 on naturally white hair at 90%,

these colors being expressed according to the Munsell notation.

Example 2

The following dye composition is prepared:

(2,3-Diamino, 5-nitro) 1-phenyl-2-propanol 0.51 g

Butoxy-2 ethanol 10 g

Tween 80 12 g

Oleic acid 20 g

2-amino-2-methyl-propanol-1 25% in water 6 g

Water qs 100 g pH = 6.4

This mixture, applied for 15 minutes at 30 ° C. on hair, gives them, after shampooing and rinsing, a coloring: 10 R 6/9 on hair bleached with white,

7.5 YR 7/4 on naturally white hair at 90%,

these colors being expressed according to the Munsell notation.

Example 3

The following dye composition is prepared:

(2,3-Diamino, 5-nitro) 1-phenyl-2-propanol 0.4 g

Butoxy-2 ethanol 12 g

Carboxymethylcellulose 2 g

Ammonium lauryl sulfate 5 g

Triethanolamine in 1% solution in water 1.5 g

Water qs 100 g pH = 7.5

This mixture, applied 20 minutes at 30 ° C on hair, gives them, after shampooing and rinsing, a coloration: 6.25 YR 6/15 on hair bleached with white,

1.25 Y 8/13 on naturally white hair at 90%, these colors being expressed according to the Munsell notation.

Example 4

The following dye composition is prepared:

(Amino-3, methylamino-2, nitro-5) phenyl-1

propanol-2 0.26 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 = 9.75

This mixture, applied for 20 minutes at 30 ° C. on hair, gives them, after shampooing and rinsing, a coloration: 5.5 YR 7/10 on hair bleached with white,

10 YR 7/6 on naturally white hair at 90%,

these colors being expressed according to the Munsell notation.

Example 5

The following dye composition is prepared:

(2,3-Diamino, 5-nitro) 2-phenyl-1-ethanol 0.6 g Methyl-2, 4-amino, 5-nitro, N- (ß, y-dihydroxy-

propyl) aniline 0.17 g Nitro-3, p-aminoethylamino-4 dihydrochloride,

N, N-bis- (P-hydroxyethyl) aniline 0.12 g

Comperlan KD 2.2 g

Lauric acid 0.8 g

Ethoxy-2 ethanol 2 g

Monoethanolamine 1.2 g

Water qs 100 g pH = 9

This mixture, applied for 15 minutes at 30 ° C on hair bleached with white, gives them, after shampooing and rinsing, a golden chestnut color.

Example 6

The following dye composition is prepared: (Amino-3, P-hydroxyethylamino-2, nitro-5)

2-phenyl-1-ethanol 0.65 g

Methylamino-3, nitro-4 phenoxyethanol 0.2 g Nitro-3, N'-P-hydroxyethylamino-4,

0.2 g N-methylaniline

Butoxy-2 ethanol 10 g

Alfol C] g / i8 8 g

Lanette wax E 0.5 g

Cemulsol B 1 g

Oleic diethanolamide 1.5 g

Monoethanolamine 20% by weight 0.3 g

Water qs 100 g pH = 9.5

This mixture, applied 20 minutes at 30 ° C to bleached hair, gives them, after shampooing and rinsing, a chestnut color.

Example 7

The following dye composition is prepared:

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

0.1g

Amino-4, nitro-3, N-P-hydroxyethylaniline

0.06 g

Methylamino-4, nitro-3, N, N-bis- (P-hydroxyethyl)

aniline

0.08 g

96% alcohol

10g

Carbopol 934

2g

5% ammonia

4g

Water qs

100 g pH = 5

This mixture, applied 20 minutes at 28 ° C on light brown hair, gives them, after shampooing and rinsing, a medium golden brown color.

Example 8

The following dye composition is prepared:

(Amino-3, methylamino-2, nitro-5)

phenyl-1 propanol-2

0.08 g p-hydroxyethylamino-2, 4-nitro phenoxyethanol

0.07 g

N - [(methylamino-4 ', chloro-3') phenyl]

2-methyl, 5-ureido benzoquinone-imine

0.06 g

N - [{(ethyl, carbamylmethyl) amino-4 '}

phenyl] methyl-2, ureido-5 benzoquinone-imine

0.052 g

96% alcohol

10g

Alfol Cu / 18

8g

Lanette wax E

0.5 g

Cemulsol B

1 g

Oleic diethanolamide

1.5g

Triethanolamine 5% by weight

3g

Water qs

100 g pH = 8

This mixture, applied 25 minutes at 35 ° C to bleached hair, gives them, after shampooing and rinsing, a medium golden brown color.

Example 9

The following dye mixture is prepared:

(2,3-Diamino, 5-nitro) 2-phenyl-1-ethanol 0.33 g

0.1 g resorcin

Metaaminophenol 0.08 g

Paraphenylenediamine 0.08 g

Paraaminophenol 0.08 g

Acetamido-3, 2,6-dimethyl phenol 0.1 g

Cemulsol NP 4 12 g

Cemulsol NP 9 15 g

Polyglycerolated oleic alcohol with 2 moles of glycerol 1.5 g

Polyglycerolated oleic alcohol with 4 moles of glycerol 1.5 g

5

10

15

20

25

30

35

40

45

50

55

60

65

669,595

Propylene glycol 6 g

Trilon B 0.12 g

Ammonia at 22 ° B 11g

Mercaptosuccinic acid 0.4 g

Water qs 100 g pH = 9.4

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

The mixture, applied 30 minutes at 28 ° C to naturally white hair at 90%, gives them, after shampooing and rinsing, a dark blond coloring.

Example 10

The following dye mixture is prepared:

(2,3-Diamino, 5-nitro) 1-phenyl-2-propanol 0.65 g

Paraphenylenediamine 0.21 g

Resorcin 0.16 g

2,4-diamino phenoxyethanol (dihydrochloride) 0.075 g

P-hydroxyethyl-amino-3, methyl-6 phenol 0.15 g

Cellosize WP 03 2 g

Ammonium lauryl sulfate 5 g

Butoxy-2 ethanol 15 g

96 ° alcohol 5 g

Ammonia at 22 ° B 10 g

Ammonium thiolactate 0.8 g

Water qs 100 g pH = 10.4

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 light brown coloring.

Example 11

The following dye mixture is prepared:

Mono-hydrochloride (3-amino, 2-methylamino,

5-nitro-1-phenyl-2-propanol

0.12g

Paraaminophenol

0.06 g

4-methylaminophenol hemisulfate

0.09 g

2-methoxy, 5-amino phenol

0.105 g

Hydroxy-7 benzomorpholine

0.05 g

N, N- (ethylcarbamylmethyl) 4-amino aniline

0.1g

Cemulsol NP 4

21g

Cemulsol NP 9

24 g

Oleic acid

4g

Butoxy-2 ethanol

3g

Ethanol at 96 °

10g

Masquol DTPA

2.5g

Thioglycolic acid

0.6g

Ammonia at 22 ° B

10g

Water qs

100 g pH = 10

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, an ashy sand coloring.

Example 12

The following dye mixture is prepared:

(Amino-3, P-hydroxyethylamino-2, nitro-5)

2-phenyl-1-ethanol 0.26 g N, N-bis- (P-hydroxyethyl) dihydrochloride

4-amino aniline 0.19 g

Resorcin 0.07 g

Amino-4 hydrochloride, 2-chloro-phenol 0.07 g

Carbamylmethylamino-3, methyl-6 phenol 0.1 g

Alfol C ^ / ig 8 g

Lanette wax E 0.5

Cemulsol B 1 g

Oleic diethanolamide 1.5 g

Masquol DTPA 2.5 g

Mercaptosuccinic acid 0.5 g

Ammonia at 22 ° B 11g

Water qs 100 g pH = 10.4

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

The mixture, applied 25 minutes at 30 ° C to reddish hair, gives them, after shampooing and rinsing, a light golden brown color.

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

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

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

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

Alfol C16 / 18 (50/50): Cetylstearyl alcohol, sold by the company Condéa.

Lanette wax E: Partially sulfated cetylstearyl alcohol, sold by Henkel.

Cemulsol B: Ethoxylated castor oil, sold by Rhône-Poulenc. Tween 80: Polyoxyethylenated sorbitol monooleate.

Lauramide: Monoethanolamide of lauric acid, sold by Witco. Comperlan KD: Coconut fatty acid diethanolamide, sold by Henkel.

Cellosize WP 03: Hydroxyethylcellulose, sold by Union Carbide. Masquol DTPA: Pentasodium salt of diethylenetriaminepen-tacetic acid, sold by Protex.

Trilon B: Ethylenediaminetetracetic acid.

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Claims (19)

669,595 1. Amino-2, nitro-4, hydroxyalkyl-6 aniline of general formula (I): • X-OH -SHR. KHR. '2 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: R ' X-OE • KHR. NO. in which R ', X and Rj have the meanings indicated above, then a selective reduction of the compound of formula (III) is carried out, either by sodium sulfide in the presence of sulfur in a hydroalcoholic solution, or by hydrogen sulfide in the presence of ammonia, or by hydrogen transfer from cyclo hexene to compound (III) in the presence of Pd / C, in an alcoholic solution. 2. Compound according to Claim 1, characterized in that X is an ethylene, propylene, 1,1-dimethyl ethylene, 1,2-dimethyl-ethylene or trimethyl-1,1,2 ethylene radical, R 'is a hydrogen atom or a methyl radical, R 1 and R 2 denote, independently of one another, a hydrogen atom, a methyl, ethyl, n-propyl, P-hydroxyethyl, y-hydroxypropyl, ß-y-dihydroxypropyl radical , aminoethyl or P-diethylaminoethyl. '2 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 may be optionally substituted by an alkyl or mono- or polyhydroxyalkyl radical, the atom d nitrogen can also be part of a beta ring, the alkyl radicals having 1 to 4 carbon atoms; R 'denotes a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms, and the cosmetically acceptable salts of this compound. 2 3 669,595 3. Compound according to claim 1 or 2, characterized in that it is chosen from the group comprising (2,3-diamino, 5-nitro) 2-phenyl ethanol-1, r [amino-3, P- hydroxyethylaminò-2, nitro-5] phenyl-2 ethanol-1, le (diamino-2,3, nitro-5) phenyl-1 propanol-2 and l (amino-3, methylamino-2, nitro-5) phenyl -1 propanol-2, as well as the salts of these compounds. 4. Process for the preparation of a amino-2, nitro-4, hydroxyalkyl-6 aniline of formula (I) according to claim 1, in which R2 represents hydrogen and Rj is defined as indicated in claim 1, characterized by reacting an aqueous ammonia solution or a primary amine of formula RjNH2 in which Rj has the same meaning as in claim 1, on a heterocyclic compound of formula: KO. 5 5. Process for the preparation of a amino-2, nitro-4, hydroxyalkyl-6 aniline of formula (I) according to claim 1, in which Rj and R2 independently denote an alkyl radical, mono - or polyhydroxyalkyl or aminoalkyl whose amine function 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 having 1 to 4 carbon atoms , characterized in that an aqueous ammonia solution or a primary amine of formula RjNH2 in which R! has the same meaning as in claim 1, on a compound of formula (IV) under the conditions defined in claim 4, the 2,4-dinitro-2,4-hydroxyalkyl aniline of formula (III) thus obtained is then subjected to the treatment defined in claim 4 to obtain the compound of formula: R ' nh2 in which R! and R ′ are 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 (IV) is carried out in the presence of protic, polar solvents or polar aprotic solvents. 7. Dye composition for keratin fibers, in particular for human hair, characterized in that it contains, in a solvent medium, at least one compound as defined in 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 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 10. Composition according to one of claims 7 to 9, characterized in that the solvents are chosen from water, lower alkanols, aromatic alcohols, polyols, glycols or glycol ethers and mixtures thereof. 11. Composition according to one of claims 7 to 10, characterized in that it also contains cosmetic adjuvants chosen from anio'nic, cationic, nonionic, amphoteric surfactants or their mixtures, thickeners, agents dispersants, penetration agents, sequestrants, film-forming agents, buffers, perfumes, basifying or acidifying agents. 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 anthraquinonics, indophenols, indoanilines and nitro derivatives of the benzene series other than those of formula (I). 13. Composition according to one of claims 7 to 11, intended to be used as styling lotion, characterized in that it is in the form of an aqueous, alcoholic or hydroalkolic solution, containing at least one cosmetic resin. 14. Composition according to one of claims 7 to 13, 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 in that it has a pH of between 7 and 11.5 and that it additionally contains a reducing agent. 15 20 25 30 35 40 45 50 55 60 65 16. A process for dyeing keratin fibers, in particular human hair, characterized in that a composition according to one of claims 7 to 12 is applied to the fibers, it is left to stand for 5 to 50 minutes, it is rinsed, washed with shampoo, rinsed again and dried. 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.