FR2574788A1 - NOVEL AMINO-2, NITRO-4, HYDROXYALKYL-6 ANILINES, PROCESS FOR THEIR PREPARATION AND THEIR USE IN DYING KERATIN FIBERS - Google Patents

Abstract

THE PRESENT INVENTION CONCERNS NEW AMINO-2, NITRO-4, HYDROXYALKYL-6 ANILINES OF FORMULA: (CF DRAWING IN BOPI) IN WHICH: X DESIGNATES A BRANCHED OR NON-BRANCHED RADICAL ALKYLENE, CONTAINING 2 TO 6 CARBON ATOMS, ONE OF THESE ATOMS MAY POSSIBLY BE SUBSTITUTED BY ONE OR MORE HYDROXYL RADICALS; R AND R INDEPENDENTLY DESIGNATE AN ATOM OF HYDROGEN, A RADICAL ALKYL, MONO- OR POLYHYDROXYALKYL OR AMINOALKYL WHOSE AMINE FUNCTION MAY BE SUBSTITUTED BY A RADICAL ALKYL OR MONO- OR POLYHYDROXYALKYL OR AMINOALKYL, WHOSE AMINE FUNCTION MAY BE SUBSTITUTED BY A RADICAL ALKYL OR MONO- OR DYO-DOSE 'NITROGEN CAN ALSO BE PART OF A HETEROCYCLE, ALKYL RADICALS CONTAINING 1 TO 4 CARBON ATOMS; R INDICATES AN ATOM OF HYDROGEN OR A RADICAL ALKYL CONTAINING 1 TO 4 ATOMS OF CARBON, AND THE COSMETICALLY ACCEPTABLE SALTS OF THESE COMPOUNDS. IT ALSO CONCERNS A PROCESS FOR THE PREPARATION OF THESE COMPOUNDS, AS WELL AS A PROCESS FOR COLORING KERATINIC FIBERS AND IN PARTICULAR HUMAN HAIR.

Description

New amino-2, 4-nitro, 6-hydroxyalkyl anilines, their process of

  preparation and their use in dyeing keratinous fibers.

  The present invention relates to novel 2-amino, nitro-

  4, hydroxyalkyl-6 anilines, their process of preparation and their use in dyeing keratinous fibers, and more particularly

human hair.

  It is well known that, in order to give the hair a direct coloration or complementary reflections in the case of coloring

  oxidation, nitrate derivatives of the benzene series can be used.

  Picnic. It has already been advocated the use of nitro-orthophenylene-

  diamines such as more particularly 2-amino, 4-nitro, 6-alkyl

  anilines in both direct dyeing and oxidation dyeing.

  However, stability has generally been noted

  insufficient light and washing of these dyes. The request

  deresse has therefore looked for new dyes with better

  their stability to light and washing, and thus it discovered the new compounds of formula (I):

02 X-OH

  (I) NBR1 NHR2 in which: X denotes a branched or unbranched alkylene radical containing 2 to 6 carbon atoms, which may be optionally substituted by one or more hydroxyl radicals; R1 and R2 denote, independently of each other, a hydrogen atom, an alkyl, mono- or polyhydroxyalkyl or aminoalkyl radical, the amine function of which may be mono- or disubstituted by an alkyl or mono- or polyhydroxyalkyl radical, nitrogen atom may also be part of a heterocycle, the alkyl radical having 1 to 4 carbon atoms;

  R 'denotes a hydrogen atom or a C1-C4 alkyl radical.

  The subject of the present invention is therefore the novel 2-amino-4-nitro-6-hydroxyalkylanilines of formula (I) indicated above,

  as well as their cosmetically acceptable salts.

  As preferred X radicals, mention may be made of the ethyl radicals

  ethylene, propylene, dimethyl-l, ethylene, dimethyl-1,2 ethylene and

methyl-1,1,2 ethylene.

  As R 1 and R 2 radicals that are more particularly preferred according to the invention, mention may be made of hydrcgene, the methyl, ethyl, n-propyl, p-hydroxyethyl, -hydroxypropyl and / or dihydroxypropyl radicals.

  aminoethyl, tb-diethylaminoethyl.

  Preferred radicals R 'according to the invention are hydrogen and

methyl radical.

  Preferred compounds of formula (I) according to the invention are: (2,3-diamino-5-nitro-2-phenyl-ethanol-1; - Lamino-3, f-hydroxyethylamino-2, 5-nitro-2-phenylethanol-1; (2,3-diamino-5-nitro) 1-phenylpropanol-2; 1 '(3-amino-2-methylamino-5-nitro) 1-phenylpropanol2,

as well as their salts.

  The subject of the present invention is also a process for prepa-

  ration of the compounds of formula (I).

  The 2-amino-4-nitro-6-hydroxyalkyl anilines of formula (I) according to the invention are prepared by a process which consists in reacting an aqueous solution of ammonia or a primary aliphatic amine R 1 NH 2 in which R 1 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 aniline of formula (III) obtained, to obtain an amino -2, 4-nitro, 6-hydroxyalkyl aniline of formula (II), which is then optionally subjected to a conventional chemical process of alkylation, hydroxyalkylation or aminoalkylation to obtain the

final compound of formula (I).

  The scheme of the process is as follows:

R 'R' R '

02N 02 2N 02 N X-OH

  + RN Reedcion I -se leut i'voe .oY NHR1 N ER

02 H2 2

(IV) (III) (II)

  R ', X and R1 having the meaning indicated above.

  This process makes it possible to obtain excellent yields of compound

final (II) or (I).

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

  dimethylformamide, dioxane, tetrahydrofuran.

  The selective reduction of the compound of formula (III) is carried out either with a hydroalcoholic solution of sodium sulphide in the presence of sulfur at a temperature of between 10 and 70 ° C., or with hydrogen sulphide in the presence of ammonia according to M. KAMEL, MI ALI and MM KAMEL, TETRAHEDRON 1966, vol. 22, p. 3353, or else by transfer of hydrogen from cyclohexene to compound (III) in the presence of Pd / C, in alcohols

  C1-C4, at a temperature between 15 C and

  by analogy with Ian D. ENTWISTLE, Robert A.W. JOHNSTENE and

  Jeffery POVALL, (J.C.S. PERKIN I (1975), 13003.

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

  wherein X and R 'have the meanings given above, which are known compounds. The nitration is carried out by adding the compound (V) to the fuming nitric acid, at a temperature of between 30 and C according to G. CHATELUS, Ann. Chem. 4, 505-547 (1949) or by adding the compound (V) to a sulfonitrile mixture, the temperature being maintained in the vicinity of 5 C, according to Charles D. HURD, Rostyslaw DOWBENKO, JACS 80, 4711-14 (1958). ). The dinitrated compound (IV) is then isolated by dilution

from the reaction medium with water.

  The compounds of formula (IV) in which X denotes the radical ethylene, propylene, dimethyl-1,1 ethylene, 1,2-dimethyl-ethylene and

  trimethyl-1,1,2 ethylene are known.

  Conventional alkylation, hydroxyalkylation or aminoalkylation processes

  used to obtain the final compound of formula (I) from the compound of formula (II) may be for example those described in patents FR 2,348,911, 2,497,662 and 2,492,370 of the applicant or other processes. classics.

  The present invention also relates to a composition

  for keratinous fibers, and more particularly for human hair, containing a 2-amino, 4-nitro, 6-hydroxy-6-aniline aniline of formula (I) above, as well as a method for dyeing keratinous fibers, and more particularly human hair, using said dye composition. The dyeing 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 may be

  for the direct dyeing of keratinous fibers or for the oxidation dyeing of these fibers, in which case the compounds of formula

  (I) confer complementary reflections on the basic coloring 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 general cosmetic vehicle.

  of water, but it is also possible to add

  compositions, organic solvents for solubilizing compounds

  those that 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 2-ethoxyethanol, ethyleneglycol,

  pylene glycol, monomethyl ether and diethylene monoethyl ether

  glycol and similar products 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 may contain anionic surfactants

  cationic, nonionic, amphoteric or mixtures thereof. These

  surfactant products are present in the compositions of the

  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 may be thickened preferably with compounds chosen from sodium alginate, gum arabic,

  derivatives of cellulose such as methylcellulose, hydroethyl

  cellulose, hydroxypropyl methylcellulose, carboxymethylcellulose and various polymers having the function of thickener such as more particularly derivatives of acrylic acid. It is also possible to use mineral thickeners 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 may also contain

  various adjuvants usually used in tincture compositions.

  for hair and in particular penetrating agents, dispersing agents, sequestering agents, film-forming agents,

tampons and perfumes.

  These compositions may be in various forms such as liquid, cream, gel or any other form suitable for

  perform a hair dye. In addition, they may be

  packaged in aerosol flasks in the presence of a propellant.

  The pH of these dyeing compositions can be between 3 and 11.5, preferably between 5 and 11.5. It is adjusted to the desired value with the aid of an alkalinizing agent such as ammonia, sodium carbonate, potassium carbonate or ammonium carbonate, hydroxides of

  sodium or potassium, alkanolamines such as mono, di-

  or triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, alkylamines such as ethylamine or triethylamine or with the aid of a acidification such as phosphoric acid, hydrochloric acid, tartaric acid, acetic acid, lactic acid

or citric.

  When the compositions are intended to be used in a direct hair dyeing process, they may contain, in addition to the compounds in accordance with the invention, other direct dyes such as azotic or anthraquinone dyes, such as, for example, tetraamine. 4,5,8-anthraquinone, indophenols, indoanilines, and nitro dyes of the benzene series differing from the compounds

of formula (I).

  Concentrations of these direct dyes other than colourants

  Formula (I) can be from 0.001 to 5% by weight

  relative to the total weight of the composition.

  These compositions, used in a direct dyeing process, are applied to the keratinous fibers during a laying time ranging 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 both to give the hair a slight coloration or reflections and to improve the holding of the setting. In this case, they

  are in the form of aqueous, alcoholic or hydro-

  alcoholics containing at least one cosmetic resin and their application

  cation is carried out on damp hair previously washed and rinsed

  which are eventually rolled up and then dried.

  The cosmetic resins used in hairsetting lotions may be in particular polyvinylpyrrolidone, crotonic acid-vinyl acetate, vinylpyrrolidone-vinyl acetate copolymers,

  maleic anhydride-butylvinyl ether, maleic anhydride-methyl ether

  as well as any other cationic polymer, anionic, not

  ionic or amphoteric usually used in this type of composition.

  These cosmetic resins are used in the compositions of the invention in a proportion of 0.5 to 4% by weight and preferably 1 to 3% by weight on the

  basis of the total weight of the composition.

  When the compositions according to the invention constitute

  oxidation processes involving the revelation by an oxidant, the compounds

  Formula (I) according to the invention are essentially

  to reflect on the final dyeing.

  These compositions then contain in combination with at least one nitro dye of formula (I) and optionally other dyes

  oxidation dye precursors.

  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- (p-methoxy)

  ethyl) paraphenylenediamine, N, N-bis (-hydroxyethyl) paraphenylene diamine, N, N- (ethyl, carbamylmethyl) amino-4 aniline, as well as

their salts.

  They may also contain para-aminophenols, for example

  example: para-aminophenol, N-methyl paraaminophenol, chloro-

  2-amino-4-phenol, 3-chloro-4-aminophenol, 2-methyl-4-amino

phenol, and their salts.

  They may also contain ortho-aminophenol.

  They may also contain heterocyclic derivatives, for example

  for example: 2,5-diaminopyridine, 7-aminobenzomorpholine.

  The compositions according to the invention may contain, in combination

  with oxidation dye precursors, couplers

  well known in the state of the art.

  As couplers, mention may in particular be made of meta-diphenols, meta-aminophenols and their salts, metaphenylenediamines and their

  salts, metaacylaminophenols, metauridophenols, metacarbal

  coxyaminophénols. Finally, we can mention other couplers that can be used in

  the compositions of the invention: O-naphthol, the couplers pos-

  sedentating an active methylene group such as diketo-

  and pyrazolones and heterocyclic couplers derived from

  pyridine and benzomorpholine.

  These compositions contain, in addition to precursors of

  oxidation agents, reducing agents present in

  between 0.05 and 3% by weight relative to the total weight

of the composition.

  The oxidation dye precursors may 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 may also be present in proportions of between 0.001 and% 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 below.

  above. The process for dyeing keratinous fibers, in particular human hair, using the revelation with an oxidant,

  consists in applying to the hair the dye composition

  taking both a dye according to the invention and dye precursors. The development of the coloration can then be carried out

  slowly in the presence of oxygen in the air, but first

  It is a chemical revealing system that is most often chosen from hydrogen peroxide, urea peroxide and persalts. We use

  in particular a solution of hydrogen peroxide at 20 volumes.

  Once the composition with the oxidizing agent has been applied to the keratinous fibers, it is allowed to stand for 10 to 50 minutes, preferably 15 to 30 minutes, after which the keratinous fibers are rinsed, washed optionally with shampoo, we rinse them

again and dry.

  The following examples are intended to illustrate the invention

  without being limiting.

PREPARATION EXAMPLE I

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

0 N / L - 0N CSEOR2

ON 2

NH3 / RCONH2 2

NO2 NO2

02 CH2CH2OH

  Reduction NH 2 lare step Preparation of (2-amino-3,5-dinitro) 2-phenyl-ethanol-1 Suspended in 350 ml of 20% ammonia and 220 ml of formamide, 0.17 mole , 7 g) 2,3-dihydro, 5,7-dinitro benzofuran

  prepared according to Chatelus An. Chem. (12), 4, 505-547 (1949).

  After 8 hours of heating at 110 ° C., 100 ml of ammonia are added.

  at 20%. The heating is maintained for 4 hours. By cooling

  dissement of the reaction medium, the expected product precipitates.

  After wringing, washing with iced water until neutral and drying under vacuum, 0.13 mol (30.3 g) of a product melting at 151 ° C. are obtained,

that is recrystallized dioxane.

  The product analysis gives the following results: Calculated Analysis for Found

C8H9N305

% C 42.29 42.24

% H 3.99 3.91

% N 18.50 18.60

% 0 35.21 35.14

  2nd step Preparation of (2,3-diamino-5-nitro) 2-phenylethanol-1

  To a suspension of 0.119 moles (27 g) of (2-amino-3,5-dinitro) phenyl-

  2-ethanol-1 in 67.5 ml of isopropanol added with an equal volume of water is added dropwise, at 60-65 C, a solution of 38.4 g

  of sodium sulphide nonahydrate and 5.4 g of sulfur in 10 ml of water.

  The heating is maintained 20 minutes after the end of the addition. On cooling, a precipitate of the expected product is obtained, which is drained, resuspended in water and then recrystallized from 96% alcohol. he

background at 172 C.

  Molecular mass calculated for C HN303: 197 8 il 3.3 Molecular weight found by potentiometric determination in the acid

  acetic acid with perchloric acid: 202.

  The analysis of the product obtained gives the following results: Calculated Analysis for Found

C8H11N303

% C 48.72 48.84

% H 5.62 5.71

% N 21.31 21.40

% 0 24.34 24.30

EXAMPLE OF PREPARATION 2

  Preparation of 1 'l mino-3, P-hydroxyethylamino-2, 5-nitro-2-phenylethanoll

0 N 0 NN2CH2OR

RHOCH2CH2NH2 t

Z HECE2CH2OH

O2 2 op N CH 2C20H Reduction

Z 2NECH2CEOR

  Step 1H Preparation of (1-hydroxyethylamino-2-dinitro-3,5) -phenyl-2-ethanol-1 0.29 moles (60.9 g) are added in portions at room temperature

  of 2,3-dihydro-5,7-dinitrobenzofuran to 122 ml of 2-aminoethanol.

  After the end of the addition, the reaction medium is brought 15 minutes

at 95 C.

  500 ml of water are added; after cooling, the expected product is filtered off, after re-capping in water and recrystallization of 75 ml.

of ethanol at 96, melts at 115 ° C.

  The analysis gives the following results: Calculated Analysis for Found

10 13 36

ZC 44.28 44.38

ZH 4.83 4.74

% N 15.49 15.48

% 0 35.39 35.60

2nd step

  Preparation of Eamino-3, A-hydroxyethylamino-2, 5-nitrophenyl

  2 ethanol-1 After adding 0.14 moles (38 g) of (2-hydroxyethylamino-2-dinitro-3,5) -phenyl-2-ethanol-1 to 530 ml of absolute alcohol added to 56 ml of ammonia at 20%, hydrogen sulfide is bubbled for 2 hours in this alcoholic solution; the temperature rises to 27 C. The bubbling is stopped. The reaction medium is carried

  during 4 hours at reflux, then it is left for 48 hours at

  ambient temperature. After concentration of the alcoholic solution half, the mineral salts are filtered. The filtrate is then evaporated to dryness. The dry residue is resuspended in isopropanol. After recrystallization

  in order to eliminate a resin, the product melts at 121 ° C.

  Molecular mass calculated for C10H15N3O4: 241 Molecular weight found by potentiometric assay in acetic acid with perchloric acid: Analysis of the product obtained gives the following results: Calculated Analysis for Found C10 15o3 4

% C 49.78 49.87

% E * 6.27 6.27

% N 17.42 17.38

% 0 26.53 26.25

EXAMPLE OF PREPARATION 3

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

02N 2N CH2CHOHCH3

N H3 / CH3OH2CR2 OH2

02 02

02N wCH CHOHCH3 E

02 2 3

NN reduction

2

  Step 1 Preparation of 1 '- (2-amino-3,5-dinitro) 1-phenylpropanol-2 The suspension was suspended in 1.1 liter of 20% ammonia and 600 ml of methylcellosolve, 0.39 mole (88%). g) 2,3-dihydro, 5,7-dinitro,

  2-methylbenzofuran prepared according to J.A.C.S. 80, p. 4711-4714 (1958).

  After 18 hours of heating at 70 ° C., the reaction medium is cooled. The formed precipitate is filtered off, which, after retacking in water until neutral, then drying in vacuo, 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 Calculated Analysis for Found

C9H1 1N305

% C 44.81 44.87

% H 4.60 4.62

% EN 17.42 17.45

% O 33.17 - 33.08

  Step 2 Preparation of (2,3-diamino-5-nitro) 1-phenylpropanol-2 To a suspension of 0.1 mole (24.1 g) of (2-amino-3,5-dinitro) phenyl 2-propanol in 60 ml of isopropanol added with an equal volume of water, a solution of 33.6 g is added dropwise at 60 ° C.

  of sodium sulphide nonahydrate and 4.8 g of sulfur in 9 ml of water.

  The heating is maintained 20 minutes after the end of the addition.

  By cooling, the expected product is obtained which is drained,

  restocked in water, and recrystallized 96 alcohol. It melts at 1740C.

  Molecular mass calculated for C9H 3N303: 211

9 13 N3 03

  Molecular weight found by potentiometric assay in acid

  acetic acid with perchloric acid: 216.

  The analysis of the product obtained gives the following results Calculated Analysis for Found

C9 13N303

% C 51.17 51.09

ZH 6,20 6,19

ZN 19.90 20.13

% 0 22.73 22.57

PREPARATION EXAMPLE 4

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

02N 02 N / H2CROHCH3

CH 3 NH 2 / EtOH

3 ^ \ '>' --ECH3

 2

02 N H2CHOHCH3

Reduction,>

\ - I NHCH, HC1

  Step 1 Preparation of (2-methylamino-3,5-dinitro) 1-phenylpropanol-2 0.056 mol (12.5 g) was suspended in 100 ml of a 33% methylamine solution in ethanol. 2,3-dihydro, 5,7-dinitro,

  2-methylbenzofuran. After stirring for 10 hours at room temperature

  biante in a clogged Erlenmeyer flask, the reaction medium is carried

  minutes to the reflux of alcohol. After cooling, the expected product

  precipitate. It is drained, washed with alcohol and then recrystallized from 50 ml of ethanol at 96 ° C. After drying, 0.047 mol (12 g) of a product is obtained.

melting at 132 C.

  The analysis gives the following results Calculated Analysis for Found

10 13 305

7C 47.06 47.11

-% I5.13 5.03

% N 16.47 16.52

% 0 31.34 31.25

  2nd step Preparation of (1-amino-3-methylamino-2-nitro-5-phenyl) -propanol-2-monohydrochloride

  After adding 0.027 mole (6.88 g) of (2-methylamino) dinitro-

  3.5) 1-phenylpropanol-2 to 100 ml of absolute ethanol added with 10.8 ml of 20% ammonia, hydrogen sulfide is bubbled for 2 h 30. After 1 hour, the temperature rises at 35 C then down. After half concentration of 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 which is recrystallized from a hydroalcoholic mixture.

  Molecular mass calculated for C 10 H 16 N 3 O 3 Cl: 261.5 Molecular weight found by potentiometric determination in water

by soda: 264.

  The analysis of the product obtained gives the following results: Calculated Analysis for Found C10o16N303C1

% C 45.89 46.00

ZE 6,12 6,13

ZN 16.06 16.21

% 0 18.35 18.38

% Cl 13.57 13.64

EXAMPLE 1

  The following dye composition is prepared: (2,3-diamino-5-nitro-2-phenyl-ethanol) 0.15 g Propylene glycol 10 g CEMULSOL NP 4 12 g CENULSOL NP 9 15 g Wheat alcohol polyglycerolated with 2 moles of glycerol 1 , 5 g Oleyl alcohol polyglycerolated with 4 moles of glycerol 1.5 g Monoglycolamine in 20% solution in water 1.5 g Water - qs 100 g pH = 10 This mixture, applied for 20 minutes at 28 ° C. on hair, gives, after shampooing and rinsing, a coloring: YR 7.5 / 8 on hair discolored to white Y 8/6 on hair naturally white to 90%, these colors being

  expressed in Munsell notation.

EXFEPLE 2

  The following dye composition is prepared: (2,3-diamino-5-nitro) 1-phenyl-2-propanol 0.51 g 2-Butoxy-ethanol 10 g TWEEN 80 12 g oleic acid 20 g 2-Amino-2-methylpropanol- 1 to 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 coloration: R 6/9 on hair discolored with white 7.5 YR 7/4 on naturally white hair at 90%, these colors being

  expressed in Munsell notation.

EXAMPLE 3

  The following dye composition is prepared: (2,3-diamino-5-nitro) 1-phenyl-2-propanol 0.4 g 2-Butoxy-ethanol 12 g Carboxymethylcellulose 2 g ammonium lauryl sulphate 5 g Triethanolamine in 1% solution in water 1.5 g Water qs 100 g pH = 7.5 This mixture, applied for 20 minutes at 30 ° C. on hair, gives them, after shampooing and rinsing, a coloring: 6, 25 YR'6 / 15 on discolored hair to white - 1,25 Y 8/13 on naturally white hair at 90%, these colors being

  expressed in Munsell notation.

EXAMPLE 4

  The following dye composition is prepared:

  (3-Amino-2-methylamino-5-nitro) 1-phenyl-2-propanol 0.26 g 9610 g Alcohol Lauramide 1.5 g Lauric Acid 1 g CELLOSIZE WP 03 5g 2 5-1 BnbTa [o apmeoumrqpla " 5u S ç'o R azlauWl ap arnD B8 891 / 9I to IoF7V S1O lpouqze Z-xoZnu 2 Z'O a '' ueI'q: aI '- u molq: amxPXq - AR' ú - xoa: 0ú 2 Z 'Ooc 2 on [Tuoqúouad 9-oxiu'x-oujm. & XqXH 2 9'0 IOUggqo z -IlUIad (ç-os; T'y-ki-ki-xoîpXtll-Eo uTmB) uAns: ao3UeATns a joza; uo -lo: sodmo 1 [al.edad no. 9 ZIJRM Xz alop au2l: abBqz uozeioloz aun 'S2e5: nT: 2uloodmeqs s-_adB' aBzJuo: analne 'nmelq ne szolODBap xnaAaqi ans DoOu eQ saznuTm çI gnblIdde azu! eIm aD3 6 = Hd 2 001O dsb nS oz S Z'l.aujmelouuqzpouoH 7 Z Ium: zp Zfxoqtlp 2 '0 fnbxaIntal p: aV s Z'z ax NvIIsIawo -ouzmIXqTiouTIi-o. -:' úoau Bap ae; pL [qtoiq3 S úr'o aul1True

  (I / do: d (d) (d) -N '.- O.zTu' z-o: 'iutmB' Z-I.n & t.

  9'0o I - ouq ll Z-oum p) Bn: aln; Atn al'xo2ulcl uolrT-psodmov el aaxdald uo Q Ilasun ap uojEB: or Be uoTas samT.Idxa ZUUZ. s [nalnoz saa 'Z06 e. svuelq lnmnamlIaanlvn xna1qa years 9 / l% 01 Duvlq ne spaolooap xneaAqi years OI / L RA 5 ': uoflBioloa an afelu: TI za gu': oodumeqs seadB 'axa8 uoz S analxnaAaqz years SoOú B sa3znU' x OZ: uepuad 9nb-FiddB ' BaueIom aD 6 = Hd

2 OO dsb nt-

  The mixture, applied for 20 minutes at 30 ° C. on bleached hair, gives them, after shampooing and rinsing, a chestnut coloring.

EXAMPLE 7

  The following dye composition is prepared: (2,3-diamino-5-nitro) 1-phenyl-2-propanol 0.1 g 4-Amino-3-nitro-N-3-hydroxyethylaniline 0.06 g 4-Methylamino nitro -3, N, N-bis (p-hydroxyethyl) aniline 0.08 g 96% alcohol CARBOPOL 934 2 g 5% ammonia 4 g Water qs 100 g pH = 5 This mixture is applied for 20 minutes at 28 ° C. light brown hair, gives them, after shampooing and rinsing, a brown coloring

golden medium.

EXAMPLE 8

  The following dyeing composition is prepared (3-amino-2-methylamino-5-nitro) 1-phenyl-2-propanol 0.08 g 2-P-hydroxyethylamino-2-nitro-phenoxyethanol 0.07 g N-E (methylamino-4 3-chloro-3'-phenyl] -2-methyl-5-ureido-benzoquinoneimine 0.06 g N- (ethyl, carbamylmethyl) amino-4'-phenyl-2-methyl-5-ureido-benzoquinoneimine 0.052 g Alcohol 96 10 g ALFOL C16 / 18 8 g Lanette wax E 0.5 g CEMULSOL B 1 g Oleic diethanolamide 1.5 g Triethanolamine 5% by weight 3 g Water qs 100O g pH = 8 This mixture, applied for 25 minutes at 35 ° C. on discolored hair, their

  gives, after shampooing and rinsing, a medium golden brown coloring.

EXAMPLE 9

  The following dye mixture is prepared: (2,3-diamino-5-nitro-2-phenyl-ethanol-1 0.33 g Resorcin 0.1 g Metaaminophenol 0.08 g Paraphenylenediamine 0.08 g Para-aminophenol 0.08 g Acetamido-3, 2,6-dimethylphenol 0.1 g CEMULSOL NP 4 12 g CEMULSOL NP 9 15 g Oleyl alcohol polyglycerolated with 2 moles of glycerol 1.5 g Oleic alcohol polyglycerolated with 4 moles of glycerol 1.5 g Propylene glycol 6 g TRILON B 0.12 g Ammonia at 22 Be 11 g Mercaptosuccinic acid 0.4 g Water qs 100 g pH = 9.4

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

  The mixture, applied 30 minutes at 28 C on natural hair

  90% white, 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 Para-phenylenediamine 0.21 g Resorcinol 0.16 g Diamino-2, 4 phenoxyethanol (dihydrochloride) 0.075 3-hydroxyethylamino-3-methyl-6-phenol 0.15 g CELLOSIZE WP 03 2 g ammonium lauryl sulphate 5 g 2-butoxy ethanol 15 g alcohol 96 5 g ammonia 22 be 10 g ammonium thiolactate 0.8 g Water qs 100 g pH = 10.4

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

  The mixture, applied for 30 minutes at 28 C on discolored hair,

  gives them, after shampooing and rinsing, a light brown coloring.

EXAMPLE

  The following dye mixture is prepared: (3-amino-2-methylamino-2-nitro-5-nitrophenyl) -propanol-2-chlorohydrate 0.12 g Para-aminophenol 0.06 g Methylamino-4-phenol-4-methyl-4-aminobromide -2, 5-amino phenol 0.105 g 7-Hydroxybenzomorpholine 0.05 g N, N- (ethylcarbamylmethyl) amino-4 aniline 0.1 g CEMULSOL NP 4 21 g CEMULSOL NP 9 24 g Oleic acid 4 g 2-Butoxyethanol 3 g Ethanol 96 10 g MASQUOL DTPA 2.5 g Thioglycolic acid 0.6 g Ammonia at 22 Be 10 g Water qs 100 g pH = 10

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

  The mixture, applied for 30 minutes at 280C on discolored hair,

  their conftere, after shampooing and rinsing, an ashen sand coloring.

EXEPLE 12

  The following dye mixture is prepared (Amino-3, β-hydroxyethylamino-2-nitro-5-phenyl-2-ethanol) 0.26 g N, N-bis (hydroxyethyl) amino-4-aniline dihydrochloride 0.19 g - 9op lgeBlJ 4B4ezD uoT; eXo1oa aun 'a2ew: 5 ja; 8auoodmeqs saide' naiajoe iuz 'al oi ns if sazolooap xna & aaq sap years DoOE e seznulm çZ gnbldde eSuleîm el samnTo oz k aalupSixo neap S 08 aznore no' Toîdmail ap zuemvm n V'oT = seca S 001 dsb neu I il aoZz 1 anbTuommv I01 S 5 anb-uTvuarnso: ldt-im apTjay 8 ç'z vaucarion ion .svR ç SI anbTalo EpNmelousq: lal Ig'llIn3 0 Sa S2SI.NVI aP a1TD ú

8 81 / 9T D I3OJV

  O0 loupq 9-m 'urmtiqnmlúmeqzeD 2 LO'0 ouLlqd Z-omolq:' -our 'mep: azmpq o: lqp 2 LO'O alrrolosaa The various trade names used in the preceding examples are explained-in more detail below. after: CARBOPOL 934: Polymer acrylic acid MW 2 to 3 million sold by Goodrich Chemical Company.

  CEMULSOL NP4: Nonylphenol with 4 moles of ethylene oxide

sold by Rhône Poulenc.

  CEMULSOL NP: Nonylphenol with 9 moles of ethylene oxide

sold by Rhône Poulenc.

ALFOL C16 /

  (50/50): Cetylstearyl alcohol sold by the

Condéa company.

  Lanette wax E: Cetyl stearyl alcohol partially

Sulphated sold by Henkel.

  CEMULSOL B: Ethoxylge castor oil sold by

Rhone Poulenc.

  TWEEN 80: Polyoxyethylenated sorbitol monooleate.

  LAURAMIDE: Monoethanolamide lauric acid sold

by Witco.

  COMPERLAN KD: Copra fatty acid diethanolamide

sold by Henkel.

  CELLOSIZE WP 03: Hydroxyethylcellulose sold by Union Carbide. MASQUOL DTPA: Pentasodium salt of diethylene acid

  pentacetic triamine sold by PROTEX.

  TRILON B: Ethylene diamine tetracetic acid.

Claims (16)

  1. Amino-2, 4-nitro, 6-hydroxy-6-aniline of general formula (I): ONA 02N X-OH He 1 (I) -5 \ NHR   In which: X denotes a branched or unbranched alkylene radical containing 2 to 6 carbon atoms, which may be optionally substituted with one or more hydroxyl radicals; R1 and R2 denote, independently of each other, 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 of nitrogen may also be part of a heterocycle, 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. Compound according to claim 1, characterized in that X is an ethylene, propylene, dimethyl-1,1 ethylene, 1,2-dimethyl-ethylene or 1,1,1-trimethyl ethylene radical, R 'is a hydrogen atom. hydrogen or a methyl radical, R1 and R2 denote independently of each other a hydrogen atom, a methyl, ethyl, n-propyl, (-hydroxyethyl) radical,   y-hydroxypropyl, t, c-dihydroxypropyl, aminoethyl or 5-diethylamino-   ethyl.' 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, 1-Eamino-3, 2-hydroxyethylamino-5-nitro-phenyl-2-phenyl   ethanol-1, (2,3-diamino-5-nitro) -phenyl-1-propanol-2 and (amino)   3, 2-methylamino-5-nitro-1-phenylpropanol-2, as well as the salts of these compounds. 4. Process for the preparation of a 2-amino-4-nitro-6-hydroxyalkyl aniline of formula (I) according to claim 1, characterized in that an aqueous solution of ammonia or a primary amine of formula R1NH wherein R has the same meaning as 3.2 i in claim 1, on a heterocyclic compound of formula (IV): 02N I0 2 N 4 C Xs (IV)   in which R 'and X have the meanings indicated in the   1, at a temperature between 20 and 120 C,   under pressure and possibly in the presence of protic solvents   polar or aprotic polar solvents to obtain a dinitrogen   2,4, 6-hydroxyalkylaniline of formula (III) R ' 15.0 2 X-O0 - 1   Wherein R ', X and R have the meanings indicated above, then selectively reducing the compound of formula (III), either with sodium sulphide in the presence of sulfur in a hydroalcoholic solution, or with hydrogen sulphide in the presence of ammonia, or by transfer of hydrogen from cyclohexene to compound (III) in the presence of Pd / C, in an alcoholic solution, to obtain the compound of formula (II): R 'ONO  2 N -OH \ NHR1 H2   and finally, an alkylation, a hydrolysis   xyalkylation or an aminoalkylation of the compound of formula (II) for obtain the compound of formula (I).   5. Dye composition for keratin fibers, and in particular   particular for human hair, characterized in that it   holds, in a solvent medium, at least one compound as defined   in any one of claims 1 to 3.   6. Composition according to claim 5, 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 any one of claims 1 to 3.   7. Composition according to claim 5 or 6, characterized in that it has a pH of between 3 and 11.5, and preferably included between 5 and 11.5.   8. Composition according to any one of claims 5 to 7,   characterized in that the solvents are selected from water, lower alkanols, aromatic alcohols, polyols,   glycols or glycol ethers and mixtures thereof.   9. Composition according to any one of claims 5 to 8,   characterized in that it additionally contains adjuvants   selected from the group consisting of antonic surfactants,   non-ionic, amphoteric or mixtures thereof, thickeners, dispersing agents, penetrating agents, sequestering agents,   film-forming agents, buffers, perfumes, alkaline agents acidifying or acidifying.   10. Composition according to any one of claims 5 to 9,   intended to be used for the direct dyeing of human hair, characterized in that it contains, in addition, other dyes   selected from among the azo dyes, anthraquin dyes   the indophenols, indoanilines and nitro derivatives of   the benzene series other than those of formula (I).   11. Composition according to any one of claims 5 to 9,   intended to be used as a setting lotion, characterized in that it is in the form of an aqueous solution,   alcoholic or hydroalcoholic, containing at least one cosmetic resin.   12. Composition according to any one of claims 5 to 7,   for use in oxidation dyeing, characterized in that it further contains at least one dye precursor by oxidation.   13. Composition according to claim 12, characterized in that it has a pH of between 7 and 11.5 and that it contains in addition a reducing agent.   14. A process for dyeing keratinous fibers, and in particular   human hair, characterized in that a composition as defined in any one of the   Claims 5 to 10, allowed to rest for 5 to 50 minutes,   rinse, wash with shampoo, rinse again and we dry.   15. A process for dyeing keratinous fibers, and in particular   human hair, characterized in that a composition as defined in the present invention is applied to the washed and rinsed fibers.   Claim 11, optionally wound up and dried.   16. A process for dyeing keratinous fibers, in particular   to bind human hair, characterized by the fact that   on fibers a composition as defined in the claims   12 and 13, optionally added with an oxidizing agent, allowed to stand for 10 to 50 minutes, rinsed, washed optionally with   shampoo, rinse again and dry.