FR2636236A1 - TINCTORIAL COMPOSITIONS FOR KERATIN FIBERS CONTAINING OXIDATION COLORING PRECURSORS AND INDOLIC COUPLERS, AND DYEING METHODS USING THE SAME - Google Patents

Abstract

Dyeing composition for keratin fibers, containing an oxidation dye precursor of the para type associated with a heterocyclic coupler of formula: (CF DRAWING IN BOPI) where R1 = H, C1 -C4 alkyl; R2 and R3, which are identical or different, denote H, C1 -C4 alkyl, carboxyl or alkoxycarbonyl; OH is in the 6 or 7 position; and / or to a salt of such a coupler. This composition makes it possible to dye the hair in a coloring having good resistance to light, to washing, to bad weather and to perspiration.

Description

Dye compositions for keratin fibers.

  containing oxidation dye precursors and indole couplers, and processings for dyeing

implementing these compositions.

  The present invention relates to novel dye compositions for keratinous fibers and in particular for human hair, containing oxidation dye precursors and indolic couplers, and a dyeing process.

  using such compositions.

  It is known to dye keratinous fibers and in particular human hair, with dyeing compositions containing oxidation dye precursors and in particular pphenylenediamines, ortho- or para-aminophenols

  generally called "oxidation bases".

  It is also known that the shades obtained with these oxidation bases can be varied by using, in combination with these bases, couplers also called color modifiers and more

  particularly aromatic meta-diamines, meta-

  aminophenols and metadiphenol1.

  It is sought in the field of hair dyeing, precursors of oxidation dyes or couplers for giving the hair, in oxidizing alkaline medium generally used in oxidation dyeing, a coloration having a satisfactory resistance to light, washing, weathering

and perspiration.

  The applicant has just discovered, which is the subject of the invention, that the use of certain indole derivatives as couplers, with para-type oxidation dye precursors, made it possible to obtain, after application on keratinous fibers and in particular the hair, dyes having resistance to light, washing, weathering and perspiration,

particularly remarkable.

  An object of the invention therefore consists of dyeing oxidation compositions, intended to be used for dyeing keratinous fibers, containing at least one para-type oxidation dye precursor with certain indole derivatives defined

below.

  Another subject of the invention is constituted by the process for dyeing keratinous fibers, in particular human hair, using a

such composition.

  Other objects of the invention will appear at

  reading the description and examples that

  follow. The oxidation dye composition according to the invention, intended to be used for dyeing keratin fibers and in particular hair, is essentially characterized in that it contains, in an acceptable solvent medium, at least one dye precursor para oxidation and at least one heterocyclic coupler, corresponding to the formula

N R3

(I):

OH

  R1 in which Oh occupies the 6 or 7 positions of the aromatic ring and R1 denotes a hydrogen atom, a C1-C4 alkyl radical; R 2 and R 3, which are identical or different, denote a hydrogen atom, a lower alkyl radical containing 1 to 4 carbon atoms, a carboxyl radical or a

  (C1-C4) alkoxycarbonyl radical; as well as their salts.

  Among the compounds of formula (I), the compounds which are particularly preferred are the compounds in which the alkyl radical denotes methyl or ethyl;

  the alkoxycarbonyl radical denotes methoxy or ethoxy-

  carbonyl. Among these compounds, there may be mentioned 6-hydroxyindole, 6-hydroxy-3-methoxycarbonylindole, 6-hydroxy-1-methyl-3-methoxycarbonylindole, 6-hydroxy-1-methyl-2,3-dimethoxycarbonyl indole, 6-hydroxy-1,2-dimethylindole, 6-hydroxy-2-methylindole, 6-hydroxy-2-carboxyindole, 6-hydroxy-2,3-dimethylindole, 6-hydroxycarboxy 3-indole, 6-hydroxy-3-ethoxycarbonylindole, 6-hydroxyethoxy-2-carbonylindole, 6-hydroxy-3-ethylindole, 6-hydroxy-1-methyl-indole, hydroxy -7 indole,

7-hydroxy-3-methylindole.

  Among these compounds, 6-hydroxy-1-methylindole and 7-hydroxy-3-methylindole are new and

  their syntheses are described below.

  Para dye precursors are compounds which are not dyes in themselves, but may be. which form a dye by a process of oxidative condensation, either on themselves or

  presence of a coupler or modifier.

  These compounds contain functional groups, in particular amino or hydroxy, in

  position relative to each other.

  These para-type dye precursors are in particular chosen from para-phenylenediamines, para-aminophenols and para-heterocyclic precursors, such as 2,5-diaminopyridine, 2-hydroxy-5-amino

  pyridine, tetra-aminopyrimidine.

  As paraphenylenediamines, there may be mentioned more particularly the compounds corresponding to formula (II) below: R8

R7 (II)

R4 X N. R6

  R5 N2 in which R4, R5 and R6, identical or different, represent an atom of hydrogen or halogen, an alkyl radical having 1 to 4 carbon atoms, an alkoxy radical having 1 to 4 carbon atoms, R7 and R8 , identical or different, represent an atom

  hydrogen, alkyl, hydroxyalkyl, alkoxy-

  alkyl, carbamrylalkyl, mesylaminoalkyl, acetylanmin

  alkyl, ureidoalkyl, carbethoxyaninoalkyl, piperidino-

  alkyl, morpholinoalkyl. These alkyl or alkoxy groups having from 1 to 4 carbon atoms, or else R7 and R8 form, together with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle under the proviso that R4 or R6 represent an atom of hydrogen when R7 and R8 do not represent an atom

  hydrogen, as well as the salts of these compounds.

  Among the compounds of formula (II), mention may be made more particularly of p-phenylenediamine, p-tolylenediamine, methoxyparaphenylenediamine, chloroparaphenylenediamine, dimethyl-2,6-p-phenylene diamine, dimethyl-2,5-paraphenylenediamine,

  2-Methoxy-5-paraphenylene-diamine, dimethyl-

  2,6-methoxy-5-para-phenylenediamine, b, N-dimethyl-para-phenylenediamine, methyl-1-amino-4-amino-N, diethyl aniline, N, N-di (β-hydroxyethyl) para-phenylenediamine, 3-methyl-amino N, N-di- (β-hydroxyethyl) aniline, 3-chloro-4-amino-N, N-di- (β-hydroxyethyl) aniline, 4-amino-N, N- (ethyl carbamylmethyl) aniline, 3-methyl-4-amino, N- (ethyl carbamylmethyl) aniline, 4-amino-N, N- (ethyl-5-piperidinoethyl) aniline, 3-methyl-4-amino-N, N- (ethyl) -piperidinoethyl ) aniline, 4-amino-N, N (ethyl E-morpholinoethyl) aniline, 3-methyl-4-amino-N, N- (ethyl-morpholinoethyl) aniline, 4-amino-N, N- (ethyl-B-acetylaminoethyl) ) aniline, 4-amino-N- (B-methoxyethyl) aniline, 3-methyl-4-amino

  N, N- (ethyl B-acetylaminoethyl) aniline, amino-4 h, h-

  (ethyl B-mesylaminoethyl) aniline, 3-methyl-4-amino

  N, N- (ethyl B-mesylaminoethyl) aniline, 4-amino N, N-

  (ethyl S-sulfoethyl) aniline, 3-methyl-4-amino N, b-

  (ethyl 8-sulfoethyl) aniline, N-amino-4 ') phenylmiorpholine, N-amino-4') phenylpiperidine. These precursors of oxidation dyes of typt para can be introduced into the dye composition, either as a free base, or 6 or form d. salts, such as in the form of hydrochloride, hydrobromide or

of sulphate.

  Among the p-aminophenols, mention may be made of p-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol and 3-chloro-4-aminophenol. 2,6-dimethyl-4-amino-phenol, 3,5-dimethyl-4-amino-phenol, 2,3-dimethyl-4-amino

  phenol, 2,5-dinamethyl-4-phenol, hydroxymethyl

  2-amino-4-phenol, 2- (4-hydroxyethyl) -amino phenol, 2-methoxy-4-amino-phenol, 3-methoxy-4-amino

phenol.

  The dyeing compositions in accordance with the invention may further contain ortho-type oxidation dye precursors, such as ortho-aminophenols, such as 1-amino-2-hydroxy-benzene, 6-methyl-1-hydroxy-2-amino-benzene, 4-methyl-1-amino-2-hydroxybenzene; orthophenylenediamines, orthodiphenols. The dyeing compositions may also contain, in addition to the heterocyclic coupler corresponding to formula (I) above, other couplers known per se, such as meta-diphenols, meta-aminophenols, meta-phenylenediamines, meta-acylaminophenols, metauridophenols, metacarbalcoxyaminophenols, α-naphthol, couplers having an active methylene group such as

  B-ketonic compounds and pyrazolones.

  By way of example, mention may be made, for example, of 2,4-dihydroxyphenoxyethanol, 2,4-dihydroxyanisole, meta-aminophenol, resorcin monomethylether, 2-methylamino-5-phenol and 2-methyl-2-N (5-hydroxyethyl) amino-5-phenol, 2-methyl-N- (p-mesylaminoethyl) amino-5-phenol,

  2,6-dimethyl-3-amino phenol, 6-hydroxybenzomorpho-

  2,4-diamino-anisole, 2,4-diamino-phenoxyethanol, 6-aminobenzomorpholine, N- (2-hydroxyethyl) amino-2-amino-47-phenoxyethanol, 2-amino-N- (B) 4-hydroxyethyl) amino-4-anisole, (2,4-diamino) phenyl, B, dihydroxypropyl ether,

  2,4-diamino phenoxyethylamine and their salts.

  It is possible to add to these compositions, as is well known in the art, the technique, in particular with a view to shade or enrich in glints the colorations provided by the oxidation dye precursors, direct dyes such as dyes azo! cs, anthraquinones or derivatives

nitrates of the benzene series.

  All of the para-type oxidation dye precursors as well as the couplers used in the dyeing compositions according to the invention preferably represent from 0.3 to 7% by weight relative to the weight of said composition. The concentration of compounds (I) can vary between 0.05 and

  3.5% by weight of the total weight of the composition.

  The acceptable solvent medium is generally aqueous and its pH can vary between 8 and 11, and it is

preferably between 9 and 11.

  It is adjusted to the desired value using an alkalinizing agent such as ammonia, alkaline carbonates, alkanolamines such as mono-,

di- or triethanolamine.

  The dye compositions in accordance with the invention also contain, in their preferred embodiment, anionic, cationic, nonionic or amphoteric surfactants or mixtures thereof. Among these surfactants, mention may be made of alkylbenzenesulphonates,

  alkylnaphthalenesulphonates, sulphates, ether

  sulfates and sulfonates; fatty alcohols, quaternary ammonium salts such as trimethylcetylammonium bromide, cetylpyridinium bromide; ethanolamides of optionally oxyethylenated fatty acids; polyoxyethylenated acids, alcohols or amines, polyglycerolated alcohols, polyoxyethylenated alkylphenols or polygl. as well as polyoxyethylenated alkyl sulphates. These surface-active agents are present in the compositions according to the invention in proportions of between 0.5 and 55% by weight and preferably between 2 and 50% by weight relative to the weight.

total of the composition.

  These compositions may also contain organic solvents for solubilizing the compounds

  that would not be sufficiently soluble in the water.

  Among these solvents, mention may be made, for example, of lower C1-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols or glycol ethers, such as butoxy-2 ethanol, ethylene glycol, propylene glycol, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol;

  analogous products or their mixtures.

  The solvents are preferably present in a proportion of between 1 and 40% by weight and in particular between 5 and 30% by weight relative to

total weight of the composition.

  The thickeners that can be added in the compositions according to the invention can be chosen in particular from sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, carboxymethylcellulose, acrylic acid polymers, xanthan gum. We can also use

  inorganic salting agents, such as bentonite.

  These thickening agents are preferably present in proportions of between 0.1% to 5% and in particular between 0.2% and 3% by weight relative to

total weight of the composition.

  The antioxidants which may be present in the compositions are chosen in particular from sodium sultite, thioglycolic acid, sodium bisulfite, ascorbic acid and hydroquinone. These antioxidants are present in the composition in proportions of between 0.05 and 1.5% by weight relative to

total weight of the composition.

  These compositions may also contain other cosmetically acceptable adjuvants, such as, for example, penetrating agents, sequestering agents, buffers, perfumes, etc. The compositions according to the invention may be in various forms, such as in the form of liquids, creams, gelb or in any other form suitable for dyeing keratinous fibers, and especially human hair. These compositions can be packaged in

  aerosol flasks in the presence of a propellant.

  The dyeing compositions in accordance with the invention containing a precursor of this para-type oxidation dye and a coupler of formula (I) are used in processes for dyeing keratin fibers and in particular human hair, according to a process involving the revelation by

an oxidizing agent.

  According to this method, the dye composition described above is mixed at the time of use with an oxidizing solution in an amount sufficient to be able to develop a coloration, and then the mixture obtained is applied to the fibers

  keratinous and in particular, human hair.

  The oxidizing solution contains oxidizing agents, such as hydrogen peroxide, urea peroxide or persalts, such as ammonium persulfate. A 20 volume hydrogen peroxide solution is preferably used. The mixture obtained is applied to the hair and allowed to stand for 10 to 40 minutes, preferably 15 to 30 minutes, after which the hair is rinsed, washed with shampoo, rinsed with

again and they are dried.

  The heterocyclic coupler of formula (I) defined above can also be used in a multistage process, consisting in one of the steps of applying the para oxidation dye precursor by means of a composition defined above. , and in another step, apply the ae coupler

formula (I).

  The oxidizing agent can be introduced just before application in the composition applied in the second stage or be added to the keratinous fibers themselves in a third step, the conditions of laying and drying or washing being identical. The examples which follow are intended to illustrate the invention without presenting a

limiting character.

EXAMPLE OF APPLICATION 1

  The following dye mixture is prepared: - 6-hydroxyindole 0.33 g - pphenylenediamine 0.27 g - Oleyl alcohol polyglycerolated with 2 moles of glycerol 4.5 g - Oleic alcohol polyglycerolated with 4 moles of glycerol 4.5 g - EThOMEEN Y 12 - ARMOCN HESS Company 4.5 g CHEMICAL Ltd (oleylamine oxyethylenated with 12 moles of ethylene oxide) - COMPERLAN KD - HENKEL Company 9.0 g (coconut diethanolamide) - Propylene glycol 4.0 g - Butoxy2 ethanol 8 , 0 g - Ethanol 96 6.0 g - MASQUOL DTPA - Company PROTEX 2.0 g (pentasodium salt of diethylene triamine pentaacetic acid) Hydroquinone 0.15 g - Sodium bisulphite solution at 35 Be 1.3 g Ammonia Be 10.0 g - Water qs 100.0 g - pH = 10.5 At the time of use, 100 g of hydrogen peroxide at 20 volumes are added. The mixture applied for 20 minutes at 34 ° C. on hair that is naturally white to 90% gives them after shampooing and rinsing, a brown coloring.

golden medium.

EXAMPLE OF APPLICATION 2

  The following dye mixture is prepared: - 6-hydroxyindole 0.33 g - paminophenol 0.27 g - oleic alcohol polyglycerolated with 2 moles of glycerol 4.5 g - oleic alcohol polyglycerolated with 4 moles of glycerol 4.5 g - ETHOMEEN O 12 - ARMOON HLSS Company 4.5 g CHENICAL Ltd (oleylamine oxyethylenated with 12 moles of ethylene oxide) - COhPERLAN RD - hENKEL Company 9.0 g (coconut diethanolamine) - Propylene Glycol 4.0 g - Butoxy-2 ethanol 8.0 g - Ethanol 96 6.0 g - MASQUOL DIPA - Company PROTEX (Pentasodium salt of diethylene triamine pentaacetic acid) 2.0 g - Hydroquinone 0.15 g Sodium bisulphite solution at 35 Be 1.3 g - Ammonia 22 Be 10.0 g Water qs 100.0 g - pH = 10.5 At the time of use, 100 g of hydrogen peroxide at 20 volumes are added. The mixture applied for 20 minutes at 34 ° C. on discolored hair confers on them after

  shampoo and rinse, a golden beige coloring.

EXAMPLE OF APPLICATION 3

  The following dye mixture is prepared: - 6-Hydroxy-1-methylindole 0.73 g - bis (B-hydroxyethyl) amino-4-aniline dihydrochloride 1.34 g CELLOSIZE ™ iP 03 - UNION CAREIDE Company 2.0 g (hydroxyethylcellulose) Ainmronium laurylsulfate 5.0 g - 2-butoxyethanol 15.0 9 - Alcohol 960 5.0 g - MASQUOL DTPA - Company PROTELX 2.0 g (pentasodium salt of diethylene triphenylpenta pentoxide) - Water qsp 100.0 g - pH = 10.5 At the time of use, 100 g of hydrogen peroxide at 20 volumes are added. The mixture applied for 20 minutes at 34 ° C. on 90% natural white hair gives them, after shampooing and rinsing, a violet-gray coloring. 14.

EXAMPLE OF APPLICATION 4

  The following dye mixture is prepared: 6-hydroxy-1-methylindole 0.29 g Paraphenylenediamine 0.22 g Octyldodecanol sold under the name EUTANGL G by the company Henkel 8.0 g Oleic acid 20.0 g Monoethanolamine lauryl ether sulphate sold under the name Siponi LM 35 by the Henkel company 3.0 g - Ethyl alcohol 10.0 g Benzyl alcohol 10.0 g - Cetyl stearyl alcohol oxyethylenated with 33 moles of ethylene oxide sold under the name of SIMULSOL GS by the company SEPPIC 2.4 g - Ethylenediamine tetracetic acid 0.2 g - Cationic polymer consisting of

recurring patterns: -

CH3 CH 3

- (CH 2) 3 - + N - (CH 2) 6 2.2 9

  CH 3 Cl 3 CH 3 Cle - Monoethanolamine 7.5 g - Linoleic acid diethanolamides sold under the name COMPERLAN F by the company Henkel 8.0 g - Ammonia 20% 10.2 g - Sodium metabisulfite in aqueous solution at 35% 1.3 g - Hydroquinone 0.15 g - Phenyl-1-methyl-3-pyrazolone -5 0.2 g - Demineralized water qs 100.0 g The composition is mixed at the time of use by weight with water oxygenated at 20

  volumes and whose ph is equal to 3.

  The mixture thus produced is applied for minutes on the gray hair at 90% white, then

  rinsed, washed, rinsed again and dried.

  The coloration obtained is beige copper blond.

EXAMPLE OF APPLICATION 5

  The following dye mixture is prepared: 6-hydroxy-2-ethoxycarbonyl-2-indole 0.41 g-Paraphenylenediamine 0.22 g-Octyldodecanol sold under the name EUTANOL G by HENKEL Co. 8.0 g-Oleic acid 20.0 g Monoethanolaniline lauryl ether sulphate sold under the name Sipon LM 35 by the company HENKEL 3.0. g - Ethyl alcohol 10.0 g Benzyl alcohol 10.0 g - cetylstearyl alcohol oxyethylenated with 33 moles of ethylene oxide sold under the name Sihmulsol GS by the company SEPPIC 2.4 g - Ethylene diamine tetracetic acid 0.2 g Cationic polymer consisting of recurring units:

-CH3 CH3

  -N - (CH 2) 3 - + r - (CH 2) 6 - 2.2 g tH 3 Cie & H 3 Cl (1 - monoethanolamine 7.5 g - linoleic acid diethanolamide sold under the name COMPERLAN F by the company HENKEL 8.0 g - 20% Ammonia 10.2 g Sodium Metabisulphite 35% aqueous solution 1.3 g - Hydroquinone 0.15 g - 1-Phenyl-3-methyl-5-pyrazolone 0.2 g - Demineralized water qs The composition is mixed at the time of use by weight with hydrogen peroxide at 20 ° C.

  volumes and whose pB is equal to 3.

  The mixture thus produced is applied for 30 minutes on gray hair at 90% white, then

  rinsed, washed, rinsed again and dried.

  The coloring obtained is beige beige cenaré.

EXAMPLE OF APPLICATION 6

  The following dye mixture is prepared: 6-hydroxy-2-carboxyindole 0.35 g Paraphenylenediamine 0.22 g Octyldodecanol sold under the name EUTANOL G by the company Henkel 8.0 g Oleic acid 20.0 g Monoethanolamine lauryl ether sulphate sold under the name Sipon LM 35 by the Henkel company 3.0 g - ethyl alcohol 10.0 g - benzyl alcohol 10.0 g - cetylstearyl alcohol oxyethylenated with 33 moles of ethylene oxide sold under the name SIMULSGL GS designation by the company SEFPIC 2.4 g - Ethylenediamine tetracetic acid 0.2 g - Cationic polymer consisting of recurring units:

H3 CH 3

  - (CH 2) 3 - + - (CH 2) 6 - 2.2 g CH 3 ClE CH 3 Cle - honoethanolamine 7.5 g Linoleic acid diethanolamide sold under the name COMPERLAN F by the company hENKEL 6.0 g - Ammonia to 20% 10.2 g - sodium hetabisulfite in 35% aqueous solution 1.3 g - Hydroquinone 0.15 g - Phenyl-1-methyl-3-pyrazolone-5 0.2 g - Demineralized Lau qs 100.0 g Composition is mixed at the time of use weight by weight with hydrogen peroxide at 20

  volumes and whose pH is equal to 3.

  The mixture thus produced is applied for 30 minutes on gray hair at 90% white, then

  rinsed, washed, rinsed again and dried.

  The color is dark blond beige copper.

EXAMPLE OF APPLICATION 7

  Example 6 is repeated using 0.29 g of 7-hydroxy-3-methylindole instead of 0.35 g.

of 6-hydroxy-2-carboxyindole.

  The dyeing conditions are identical to

those of Example 6.

  The hair is dyed in light blond iridescent mahogany.

EXAMPLE OF APPLICATION 8

  Example 6 is repeated using 0.32 g of 6-hydroxy-2,3-dimethylindole instead of 0.35 g.

of 6-hydroxy-2-carboxyindole.

  The dyeing conditions are identical to

those of Example 6.

  The hair is dyed in light iridescent blonde.

EXAMPLE OF APPLICATION 9

  The following dyeing mixture is prepared - 7-hydroxy-indole 0.27 g - pphenylenediamine 0.22 g - Octyldodecanol sold under the name EUTANGL G by the company iENKEL 8.0 g - Oleic acid 20.0 g Lauryl ether sulphate monoethanolamine sold under the name Sipon LM 35 by the company HENKEL 3.0 g - Ethyl alcohol 10.0 g - Benzyl alcohol 10.0 g - cetylstearyl alcohol oxyethylenated with 33 moles of ethylene oxide sold under the name SIMULSOL GS by the company SEPPIC 2.4 g - Ethylenediamine tetracetic acid 0.2 g - Cationic polymer consisting of recurring units: CH3 CH 3 7 ± (CH 2) 3 - + N - (CH 2) 6 2.2 g CH 3 Cl 1 H 3 Cl Monoethanolamine 7.5 g - linoleic acid diethanolamide sold under the name COMPERLAN F by the company HENKEL 8.0 g - 20% ammonia 10.2 g - sodium hetabisulphite in 35% aqueous solution 1.3 g - Hydroquinone 0.15 g - Phenyl-1-methyl-3-pyrazolone-5 0.2 g - Demineralized water e qs 100.0 g The composition is mixed at the weight by weight with use of hydrogen peroxide at 20

  volumes and whose ph is equal to 3.

  The mixture thus produced is applied for 30 minutes on gray hair at 90% white, then

  rinsed, washed, rinsed again and dried.

  The coloring is dark ashy dark ash.

EXAMPLE OF APPLICATION 10

  The following dye mixture is prepared: - 7-hydroxy-indole 0.53 g - pamphenophenol 0.44 g - Octyldodecanol sold under the name EUTANOL G by the company HENKEL 8.0 g - Oleic acid 20.0 g - Lauryl ether sulphate monoethanolamine sold under the name Sipon LM 35 by the company HENKEL 3.0 g - ethyl alcohol 10.0 g - benzyl alcohol 10.0 g - cetylstearyl alcohol oxyethylenated with 33 moles of ethylene oxide sold under the name SIMULSOL GS by the company SEPPIC 2.4 g - Ethylenediamine tetracetic acid 0.2 g - Cationic polymer consisting of recurring units:

 H3 CH3

  2.2 g CH 3 ClP CH 3 C 5 - Monoethanolamine 7.5 g Linoleic acid diethanolamide sold under the name COMPERLAN F by the company Henkel 8.0 g - 20% Ammonia 10.2 g - 35% aqueous sodium metabisulphite 1.3 g - Hydroquinone 0.15 g - 1-Phenyl-3-methyl-5-pyrazolone 0.2 g - Demineralized water qbp 100.0 The composition is mixed at the time of use by weight with hydrogen peroxide at 20 ° C.

  volumes and whose pH is equal to 3.

  The mixture thus produced is applied for minutes on the gray hair at 90% white, then

  rinsed, washed, rinsed again and dried.

  The color is coppery blonde pearly.

EXAMPLE OF APPLICATION 11

  90% white locks of hair are dyed with a composition (A9) having the following composition: - 6-hydroxyindole 2.0 g - Ethanol 10.0 g Sodium lauryl ether sulphate 1.0 g - Water qs 100.0 g The exposure time is 10 minutes. This gives, after rinsing and drying, a gray wick with golden highlights. Then applying for 3 minutes a mixture of equal amounts of a 0.5% solution of N, N-bis-hydroxyethylparaphenylenediamine in water and 6% hydrogen peroxide (pH about 7). after rinsing and drying, a wick colored blond

dark with purple hues.

EXAMPLE OF APPLICATION 12

  A hydroalcoholic solution containing 2.5% of 6-hydroxy-indole ph (NaOH) is prepared which is applied to hair at a rate of 2.5 g per g of gray hair. We obtain after a 10 minutes exposure, rinsing and

  drying, gray hair slightly ashy.

  If a mixture is then applied

  equivalents of a 0.5% solution of N-methoxyethylpara

  phenylenediamine at pH 10 and hydrogen peroxide at 6%, for 3 minutes, after rinsing and drying,

  light brown hair.

PREPARATION EXAMPLE 1

  Preparation of 6-hydroxy-1-methylindole

1st step:

  Preparation of 6-benzyloxy-1-methylindole

  To 125 g of pelletized sodium hydroxide in 125 ml of water, 300 ml of toluene, 50 ml of

  methyl and 7.36 g of tetrabutyl hydrogen sulphate

  ammonium, then, with stirring, 0.33 moles (73.6 g) of 6-benzyloxyindole. After the end of the exotherm, stirring is maintained for 15 minutes. The reaction medium is diluted with two volumes of water. After separation of the organic phase, the aqueous phase is extracted with toluene. By evaporation, after washing with water and drying of the organic phases, the product is obtained

expected. It melts at 79 C.

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

C16H15NO

C 81.01 80.92

H 6.33 6.36

N, 5.91, 5.80

0 6.75 6.99

2nd step:

  Preparation of 6-hydroxy-1-methylindole

  The mixture consisting of 0.24 moles (57 g) of 6-benzyloxy-1-methylindole, 5.7 g of 10% palladium-on-charcoal, 114 ml of cyclohexene and 170 ml of ethanol was refluxed for 30 minutes. 96. Filtered hot to remove the catalyst. After evaporation in vacuo of the filtrate, an oil is obtained which, solubilized in isopropyl ether, is brought after evaporation to

  dry, to the expected product. It melts at 74 C.

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

C9E9NO

C 73.47 73.57

H 6.12 6.12

N, 9.52 9.39

O 10.88 11.07

EXAMPLE OF PREPARATION 2

  Preparation of 7-hydroxy-3-methylindole

  1st step: Preparation of LTbenzyloxy-3'-chloro-5'-nitro-2'1) phenyl7-1

cyano-2 propane.

  The reaction mixture is stirred under reflux for 8 hours at a temperature of 0.5 mol (151.2 g) of 3-benzyloxy-5-chloro-2-nitrophenylacetonitrile, 152.6 g of methyl iodide and 207 g of toluene. potassium carbonate in 500 ml of acetone. The reaction medium is diluted with 4 kg of ice water with 500 ml of acetic acid. The expected product precipitates. After

  recrystallization of acetic acid, it melts at 180 C.

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

C16H13N203C1

C 60.67 60.72

H 4.14 4.12

N 8.84 8.64

0 15.15 15.01

Cl 11,19 11,34 2nd stage:

  Preparation of 7-hydroxy-3-methylindole

  The reaction mixture consisting of 20 g of CTbenzyloxy-3 was refluxed for 4 hours. 5'-chloro-5'-nitro-2 ') phenyl-1-cyano-2 propane, 10 g of 10% palladium on charcoal in 100 ml of ethanol and 40 ml of cyclohexene added. At the end of the reaction, the catalyst is separated from the reaction medium by filtration. After addition of carbon black to the filtrate, filtration and evaporation, the expected product is obtained which crystallizes from an ethereal mixture.

  isopropyl-chloroform. It melts at 190 C.

  The analysis of the product obtained gives the following results: Calculated Analysis for Irouvé C9H9gNO

C 73.45 73.53

H 6.16 6.23

N, 9.52 9.45

O 10.87 10.76

Claims (20)

  1. Dyeing composition for keratinous fibers, characterized in that it contains in a medium suitable for dyeing these fibers, at least one para type oxidation dye precursor in combination with at least one heterocyclic coupler corresponding to the formula: R3 R2 1   OHf R1 in which OH occupies the 6 or 7 positions of the aromatic ring and R1 represents a hydrogen atom, a C1-C4 alkyl radical; R2 or R3, which may be identical or different, denote a hydrogen atom, a lower alkyl radical containing from 1 to 4 carbon atoms, a carboxyl radical or a   (C1-C4) alkoxycarbonyl radical; as well as their salts.   2. Composition according to Claim 1, characterized in that the compounds of formula (I) are chosen from 6-hydroxyindole, 3-hydroxy-3-methoxycarbonylindole and 6-hydroxy-1-methyl-3-methoxycarbonylindole. , 6-hydroxy-1-methyl-2,3-dimethoxycarbonylindole, 6-hydroxy-dimethyl-1,2-indole, 6-hydroxy-2-methylindole, 6-hydroxy-2-carboxyindole, 6 2,3-dimethylindole, 6-hydroxy-3-carboxyindole, 3-hydroxyethoxycarbonylindole, 6-hydroxy-2-ethoxycarbonylindole, 3-hydroxy-3-methylindole, 6-hydroxyethyl -1 indole, 7-hydroxyindole, 7-hydroxy 3-methylindole.   3. Conposition according to any one of   1 or 2, characterized in that the   para-type oxidation dye precursors are   chosen from paraphenylenediamines, para-   aminophenols, heterocyclic precursors para.   4. Composition according to any one of   claims 1 to 3, characterized in that the   paraphenylenediamineb are chosen from compounds of formula (II) 8 R7 (II) R4 XR6 R \ v H2   in which R4, R5 and R6, identical. or different, denote a hydrogen or halogen atom, an alkyl radical having 1 to 4 carbon atoms, an alkoxy radical having 1 to 4 carbon atoms, R7 and R8, identical or different, denote a hydrogen atom , an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl or ureidoalkyl radical,   carbethoxyaminoalkyl, piperidinoalkyl, morpholino-   alkyl, these alkyl or alkoxy groups having 1 to 4 carbon atoms, or R7 and R8 form, together with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle, with the proviso that R4 or R6 represent a hydrogen atom when R7 and R8 do not represent a hydrogen atom, as well than the salts of these compounds.   5. Composition according to claim 4, characterized in that the compounds of formula (II) are chosen from p-phenylenediamine, ptoluylenediamine, methoxyparaphenylenediamine, chloroparaphenylenediamine, dimethyl-2,6-p-phenylene dianmin, dimethyl -2,5 paraphenylenediamine, the   2-Methoxy-5-para-phenylenediamine, dimethyl-   2,6-methoxy-5-paraphenylenediamine, N, N-dimethyl-para-phenylenediamine, 3-methyl-4-amino-4-b, N-diethylaniline, N, N-di (B-hydroxyethyl) para-phenylenediamine, 3-methyl-4-amino N, N-di- (B-hydroxyethyl) aniline, 3-chloro-4-amino-N, N-di- (2-hydroxyethyl) aniline, 4-amino-N- (ethyl carbamylmethyl) aniline, methyl 3-amino-4-N, h- (ethyl carbamylmethyl) aniline, 4-amino-b, N- (ethyl-8-piperidinoethyl) aniline, 3-methyl-4-amino-N, N- (ethyl-3-piperidinoethyl) aniline , 4-amino-N, N- (ethyl-morpholinoethyl) aniline, 3-methyl-4-amino-N, N- (ethyl-α-morpholinoethyl) aniline, 4-amino-N, N- (ethyl 8-acetylaminoethyl) aniline, amino-4-N- (amethoxyethyl) aniline, methyl-3-amino-4   N, N- (ethyl 8-acetylaminoethyl) aniline, 4-amino N, N-   (ethyl B-mesylaminoethyl) aniline, 3-methyl-4-amino   N, N- (ethyl B-mesylaminoethyl) aniline, 4-amino N, N-   (ethyl-sulfoethyl) aniline, 3-methyl-4-amino-N, N-   (ethyl B-sulfoethyl) aniline, N-Tamino-4 ') phenyl morpholine, NLTarino-4') phenylpiperidine and their salts. 6. Composition according to any one of   claims 1 to 4, characterized in that the   p-aminophenols are chosen from p-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-chloro-4-aminophenol and 2-dimethyl, 6-amino-4-phenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-amino phenol, 2-hydroxymethyl-4-amino phenol, (2-hydroxyethyl) -2-amino-phenol, 2-methoxy-4-amino   phenol, 3-methoxy-4-amino phenol.   7. Composition according to any one of   claims 1 to 6, characterized in that the   The composition further contains ortho-type oxidation dye precursors selected from ortho-aminophenols, orthophenylenediamines and orthodiphenols. 8. Composition according to any one of   claims 1 to 7, characterized in that the   The composition also contains, in addition, heterocyclic couplers of formula (I), meta-diphenols, meta-aminophenols, meta-phenylenediamines, meta-acylaminophenols, metauridophenols, metacarbalcoxyaminophenols, O-naphthol, B-ketones and pyrazolones.   9. Composition according to Claim 8, characterized in that the couplers different from the heterocyclic couplers of formula (I) are chosen from 2,4-dihydroxy phenoxyethanol, 2,4-dihydroxyanisole, meta-aminophenol, monomethyl ether and resorcinol, 2-methyl-5-aminophenol, 2-methyl-N- (β-hydroxyethyl) amino-5-phenol, 2-methyl-N- (B-mesylaminoethyl) amino-5-phenol,   2,6-dimethyl-3-amino-phenol, 6-hydroxybenzomorpho-   2,4-diamino-anisole, 2,4-diamino-phenoxyethanol, 6-aminobenzomorpholine, N- (β-hydroxyethyl) amino-2-amino-7-phenoxyethanol, 2-amino-N- (B) 4-hydroxyethyl) -4-amino anisole, (2,4-diamino) phenyl, B ', dihydroxypropyl ether,   2,4-diamino phenoxyethylamine, and their salts.   10. Composition according to any one of   Claims 1 to 9, characterized in that the   composition also contains direct dyes.   11. Composition according to any one of   Claims 1 to 10, characterized in that   para type oxidation dyes and coupleurb are present in proportions of between 0.3 and 7% by weight relative to the total weight of the composition. 12. Composition according to any one of   Claims 1 to 11, characterized in that the   compound of formula (I) is present in proportions of between 0.05 and 3.5% by weight relative to total weight of the composition.   13. Composition according to any one of   claims 1 to 12, characterized in that the   medium suitable for dyeing these fibers is   aqueous and has a pH of between 8 and 11.   14. Composition according to any one of   claims 1 to 13, characterized in that the   The composition also contains anionic, cationic, nonionic, amphoteric or their mixtures.   15. Composition according to any one of   claims 1 to 14, characterized in that the   composition also contains organic solvents in proportions of between 1 and 40% by weight   relative to the total weight of the composition.   16. Composition according to any one of   Claims 1 to 15, characterized in that the   The composition also contains thickeners, antioxidants, penetrating agents,   sequestering agents, tampons and / or perfumes.   17. Composition according to any one of   claims 1 to 16, characterized in that   is in the form of liquids, creams and gels and is optionally packaged in aerosols in the presence of a propellant.   18. Process for the preparation of a dye composition intended to be applied immediately to human hair, characterized in that the dye composition defined in any one of the two compositions is mixed at the time of use.   1 to 17, with an oxidizing solution in one   enough to form a dye.   19. Process for dyeing keratinous fibers, in particular human hair, characterized in that a composition as defined in any one of the   1 to 17, on said fibers, in the presence   of an oxidizing agent, that the composition is left in contact with the fibers for 10 to 40 minutes, that the application is followed by rinsing the hair, an washing, rinsing and drying.   20. A process for dyeing keratinous fibers, in particular human hair, characterized in that the precursor of the para oxidation dye is applied in one of the steps, and in another step at least one heterocyclic coupler of formula (I), the oxidizing agent being introduced just before use, either in the composition applied in the second time, or   added to the fibers in a third time.