AU672586B2 - Dyeing composition based on hydroxyindoline derivatives - Google Patents

Abstract

The use of a hydroxyindoline derivative of formula (I), wherein R1? is hydrogen or C1-4? alkyl; R2? is hydrogen or C1-4? alkyl; OH and -OR2? are in positions 4, 5, 6 or 7, with the proviso that when they are in positions 5 and 6, R2? is alkyl; and acid addition salts thereof; for dyeing keratin-containing matter, particularly human keratin-containing matter, is described.

Description

OPI DATE 05/04/93 AOJP DATE 10/06/93 APPLN. ID 26499/92 ii111(ii111111111iiII PCT NUMBER PCT/FR92/00856 II~11 I I AU9226499 DEMANDE INTERNATIONALE PUBLIEE EN VE.RTU DU YRA IIL L WIPEKA I UN LN MAI I L~t Ut iR~vtTS (PCT) (51) Classification internationale des brevets 5 (11) Numniro de publication internationale: WO 93/05018 C07D 209/08, A61 K 7/13 Al (43) Date de publication internationale: I8 mars 1993 (18.03.93) (21) Num~ro de la demnande internationale: PCT/FR92/00856 (74) Mandataire: BUREAU D.A. CASALONGA; 8, avenue Percier, F-75008 Paris (FR).

(22) Date de d~p6t international: I I septembre 1992 (11.09.92) (81) Etats d~sign~s: A U, CA, JP, KR, US, brevet europ~en (AT, Donnees inelatives i la priorit6: BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, 91/11281 12 septembre 1991 (12.09.91) FR NL, SE).

(71) Deposant (pour tous les Etats d~sign~s sauf US): L'OREAL Publike [FR/FR]; 14, rue Royale, F-75008 Paris Ai'ec rapport de recherche jaternationale.

(72) Inventeurs; et Inventeurs/D~posants (US seutlemnent) LAGRANGE, Alain [FR/FRI; 5, rue de Montry-Coupvray, F-77700 Serris LUPPI, Bernadette [FR/FR); 43, rue Berlioz, F- 93270 Sevran JUNINO, Alex~ [FR/ FRI; 16, rue Docteur-Bergoni F-93180 Livry-Gargan (FR).

(54)Title: DYEING COMPOSITION BASED ON HYDROXYINDOLINE DERIVATIVES (54)Titre: COMPOSITION TINCTORIALE A BASE DE DERIVES D'HYDROXYINDOLINE CH 2

R

2 0c N& 2 (57) Abstract The use of a hydroxyindoline derivative of formula wherein R, is hydrogen or C 1 4 alkyl; R 2 is hydrogen or C 1 4 alkyl; OH and are in positions 4, 5, 6 or 7, with the proviso that when they are in positions 5 and 6, R 2 is alkyl; and acid addition salts thereof; for dyeing keratin-containing matter, particularly human keratin-containing matter, is described.

(57) Abrig6 L'invention est relative d l'utilisation pour la teinture des mati~res k~ratiniques, en particulier les matieres keratiniques humaines, d'un d&riv6 d'hydroxyindoline repondant A la formule dans laquelle: R, repr~sente un hydrog~ne ou un alkyle en

C

1

-C

4

R

2 repr~sente un hydrog~ne ou un alkyle en C 1

-C

4 OH et -OR 2 occupent les positions 4, 5, 6 ou 7, sous reserve que lorsqu'ils occupent les positions 5 et 6, R 2 d~signe alkyle; ainsi que leurs sels d'addition d'acides.

Hydroxyindoline derivative based dye composition, method of dyeing keratinous fibers and novel hydroxyindoline derivatives The present invention concerns the use of hydroxyindoline derivatives in dyeing keratinous fibers, in particular human keratinous fibers such as hair, dye compositions, dyeing methods using these compounds, and novel hydroxyindoline derivatives.

In the past, hair dyes have used certain nmonohydroxyindolines or monoaminoindolines as couplers as described, for example, in French patent FR-A-2 008 797.

United States patent US-A-4 013 404 describes mono- or diaminoindolines or monohydroxyindolines as oxidation base or couplers for use in dyeing hair.

It is further known to use dyes from the indole family, in particular 5,6-dihydroxyindole, to dye keratinous fibers such as human hair, as shown in particular in French patents FR-A-1 133 594 and FR-A-1 166 172.

We have discovered that hydroxyindoline derivatives, particularly in the salt form, are particularly stable in the normal media employed for dyeing keratinous iibers when compared with the known compound 5,6-dihydroxyindole.

In addition, these compounds are more soluble in water than 5,6-dihydroxyindole.

We have established that these compounds oxidize particularly easily in alkaline solution and can be used for dyeing hair without the need for an oxidizing agent, thus enabling a wide range of more or less intense shades to be obtained.

The invention thus consists in the use of hydroxyindoline derivatives and their saits having formula defined below, in the dyeing of keratinous fibers, in particular hair.

The invention also provides dye compositions for use in dyeing keratinous fibers, in particular human hair, containing at least one hydroxyindoline derivative having formula as defined below.

The invention further consists in dyeing methods using these compounds.

Further objects of the invention will become apparent from the following description and examples.

In accordance with the invention, hydroxyindoline derivatives for dyeing keratinous fibers, in particular human keratinous fibers such as hair, are characterized in that they have the following formula:

HO

CH RO 2 R20CH 2

R

where:

R

1 represents a hydrogen atom or a C 1

-C

4 alkyl group;

R

2 represents a hydrogen atom or a C 1

-C

4 alkyl group; the OH and -OR 2 groups are in the 4, 5, 6 or 7 positions on the benzene ring, provided that, when in the 5 and 6 positions, R 2 represents a C 1

-C

4 alkyl group; and acid addition salts of these compounds.

Hydrochlorides and hydrobromides of these compounds are preferred.

Preferred compounds for use in the present invention are selected from the following: 7-methoxy 6-hydroxyindoline, 6,7-dihydroxyindoline, 5-hydroxy 4-methoxyindoline, 5-methoxy 6-hydroxyindoline, 7-hydroxy 6-methoxyindoline, 7-methoxy 4-hydroxyindoline, 4-hydroxy 5-hydroxy 6-methoxyindoline, 4,7-dihydroxyindoline.

The hydrobromides of these compounds are particularly preferred.

Particular compounds having formula where R 2 represents an alkyl group, can be prepared by debenzylation of the corresponding alkoxybenzyloxyindoline in the presence of hydrobromic acid at a temperature of less than or equal to 40*C, in accordance with the following reaction scheme: BzO

HO

R CH HBr R

O

/CH2

R

2 0x 2 R0 2

R

(IA)

(I)

SCHEME A N-alkylbenzyloxyalkoxyindolines with formula (II), where R 1 represents a C 1

-C

4 alkyl group, can be prepared by conventional alkylation of the benzyloxyalkoxyindoline using an alkyl halide or a dialkyl sulfate.

N-alkylhydroxyalkoxyindolines with formula (IA) can be prepared by direct alkylation of the corresponding hydroxyalkoxyindoline.

Particular compounds with formula (IB) where R 2 represents a hydrogen atom can be prepared as follows: either by dealkoxylation of compounds (IA) using hydrobromic acid at a temperature greater than or equal to or by demethylation of the corresponding dimethoxyindoline using hydrobromic acid at a temperature greater than or equal to 80 0 C in accordance with the following reaction scheme:

OCH

3

HO

H HBr C H 2

CH

3 0H 2 H Ho R1

(B)

(ID (m) SCHEME B Dimethoxy N-alkylindolines with formula (III) where

R

1 represents a C 1

-C

4 alkyl group can be prepared as follows: either by conventional alkylation of the dimethoxyindoline using an alkyl halide or dialkyl sulfate; or by reduction of dialkoxyindoles with sodium borohydride in the presence of a carboxylic acid using the method described by GRIBBLL in J A C S 1974, 96, 7812.

Dihydroxy N-alkylindolines with formula (IB) can be prepared by direct alkylation of the dihydroxyindoline with the exception of 5,6-dihydroxyindoline.

Hydrobromides of hydroxyindoline derivatives with formula are novel compounds and constitute an object of the invention. They are prepared using the methods indicated above.

These compounds are particularly stable when stored under normal storage conditions for keratinous fiber dye compositions.

The invention still further consists in two novel compounds: 6-hydroxy 7-methoxyindoline, 6,7-dihydroxyindoline, and salts thereof.

Hydroxyindoline derivatives with formula as defined above are generally used in compositions which constitute a further object of the invention.

In accordance with the invention, dye compositions for use in dyeing keratinous fibers, in particular human keratinous fibers such as hair, are characterized in that they contain at least one hydroxyindoline derivative having formula defined above in an appropriate dye medium.

The quantity of hydroxyindoline derivative with formula used in the composition is generally between proportions of 0.01% to 8% by weight, preferably 0.03% to by weight with respect to the total composition weight.

The compositions can have a number of different forms, in particular a thick or thin lotion, a cream, a foam or a gel, and may be packaged as an aerosol.

They may also constitute one element of a dye means having several components in a device comprising a plurality of compartments or dye kit.

The appropriate dye medium is preferably an aqueous medium which must be cosmetically acceptable when the compositions are used to dye living human hair. This aqueous medium may be water or a water/solvent(s) mixture.

The pH of the composition is between 3 and 12.

The solvents are selected from organic solvents, preferably ethyl alcohol, propyl or isopropyl alcohol, tertiobutyl alcohol, ethyleneglycol, monomethyl, monoethyl and monobutyl ethers of ethyleneglycol, ethyleneglycol monoethylether acetate, propyleneglycol, propyleneglycol and dipropyleneglycol monomethylethers and methyl lactate.

Particularly preferred solvents are ethyl alcohol, propyleneglycol and ethyleneglycol monobutylether.

Compounds in accordance with the invention have the advantage of being able to be used in a substantially aqueous medium.

A medium constituted by anhydrous solvents selected from the solvents defined above can also be used. In this instance, the solvent is either mixed with the aqueous medium just before use or is applied to keratinous fibers which have been previously moistened with an aqueous composition.

Within the context of the invention, an anhydrous solvent is one containing less than 1% water.

When the appropriate dye medium is a water/solvent(s) mixture, the solvents are used in concentrations of between 0.5% and 75% by weight with respect to the total composition weight, preferably in proportions of less than 20% by weight.

Compositions in accordance with the invention may contain additives which are normally used in dyeing keratinous fibers, in particular cosmetically acceptable additives, when these compositions are used to dye living human hair.

These compositions can in particular contain fatty amides, preferably in proportions of 0.05% to 10% by weight, anionic, cationic, non-ionic or amphoteric surfactants or mixtures thereof, preferably in proportions of between 0.1% and 50% by weight, thickening agents, perfumes, sequestrating agents, film-forming agents, treatment agents, dispersing agents, packaging agents, preservatives, opacifiers and keratinous fiber swelling agents.

The thickening agents are selected from sodium alginate, gum arabic, guar gum, heterobiopolysaccharides such as xanthane gum, scleroglucanes, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, the sodium salt of carboxymethylcellulose and acrylic acid polymers, preferably crosslinked.

Mineral thickening agents such as bentonite can also be used.

The thickening agents are used alone or mixed together and are preferably present in proportions of between 0.1% and 5% by weight with respect to the total composition weight, advantageously between 0.5% and 3% by weight.

Alkalinizing agents which can be used in the compositions are amines such as alkanolamines, alkylamines and alkaline or ammonium hydroxides or carbonates.

Acidification agents which can be used in these compositions may be selected from lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid and citric acid.

It is, of course, possible to use any other cosmetically acceptable alkalinizing or acidification agent, particularly when dyeing hair.

When using a foam composition, it may be packaged unuer pressure in an aerosol container in the presence of a propellant and at least one foam-forming agent.

Foam-forming agents can be selected from anionic, cationic, non-ionic or amphoteric polymeric foaming agents or mixtures thereof or surfactants as defined above.

A method of dyeing keratinous fibers, in particular human keratinous fibers, constitutes a further object of the invention and is characterized in that it consists in applying to the fibers a composition as defined above and containing at least one hydroxyindoline derivative with formula as defined above in an appropriate dye medium, leaving the composition in contact with the fibers for a sufficient time for the color to develop, either in air or using an oxidizing system, then rinsing and if necessary washing the dyed fibers.

According to a first embodiment of the invention, the fibers are dyed without adding an external oxidizing agent, simply by contact with air.

According to a further embodiment of the invention, the color is developed using a chemical oxidizing system selected from: iodide ions and hydrogen peroxide, composition containing the hydroxyindoline derivative with formula additionally containing in this case either iodide ions or hydrogen peroxide, and application of composition is preceded or followed by application of composition containing, in an appropriate dye medium, either: hydrogen peroxide at a pH of between 2 and 12, preferably between 2 and 7, when composition contains iodide ions, or: iodide ions at a pH of between 3 and 11 when composition contains hydrogen peroxide; (ii) application of composition containing the hydroxyindoline derivative with formula being followed by application of an aqueous composition (B) having an acidic pH, composition or composition (B) containing at least one nitrite; (iii) oxidizing agents selected from hydrogen peroxide, periodic acid and its hydrosoluble salts, sodium hypochlorite, chloramine T, chloramine B, potassium ferricyanide, silver oxide, Fenton's reagent, lead (IV) oxide, cesium sulfate, ammoi.ium persulfate and alkaline chlorites; these oxidizing agents being present in composition containing the hydroxyindoline derivative with formula or applied simultaneously or sequentially by means of a composition containing them in an appropriate dye medium; (iv) metal anions selected from permanganates or bichromates, the oxidizing agents being applied by means of an aqueous composition at a pH of 2 to 10 before application of composition salts of metals from groups 3 to 8 of the periodic table, these metal salts being applied by means of a composition containing them in an appropriate dye medium, composition being applied before or after application of composition (vi) rare earth salts applied by means of a composition containing them in an appropriate dye medium, composition being applied before or after application of composition containing the hydroxyindoline derivative with formula (vii) a quinone derivative selected from ortho- or parabenzoquinones, ortho- or parabenzoquinone monoimines or diimines, 1,2- or 1,4-naphthoquinones, orthoor parabenzoquinone sulfonimides, a,w-alkylene-bis- 1,4-benzoquinones or 1,2 or 1,4-naphthoquinone monoimines or diimines by means of a composition containing them in an appropriate dye medium, the hydroxyindoline derivative with formula and quinone derivatives being selected so that the difference in oxidoreduction potential AE between the oxidoreduction potential Ei of the hydroxyindoline derivative with formula (I) determined voltametrically at pH 7 in a phosphate medium on a vitreous carbon electrode and the oxidoreduction potential Eq of the quinone derivative determined polarographically at pH 7 in a phosphate medium on a mercury electrode with reference to a saturated calomel electrode is such that: iAE =Ei -Eq 320 millivolts; composition being applied either before or after application of composition containing the hydroxyindoline derivative with formula In a preferred embodiment of the invention, application of compositions and is separated by a water rinse step.

The following quinone derivatives can be used in the method: 1, 4-benzoquinone, 2-methoxy l,4-benzoquinone, 2-methyl l,4-benzoquinone, 2,6-dimethyl l,4-benzoquinone, 2,3,5-trichloro 6-methyl l,4-benzoquinone, 2-acetylamino l,4-benzoquinone, 2-acetylamino 3,5-dimethyl 1,4-benzoquinone, 2,6-dimethyl 5-acetylamino 1,4-benzoquinone, 2-chloro 1,4-benzoquinone, tetrachloro 1,2-benzoquinone, 2,3-dimethoxy 1,4-benzoquinone, 2-1-carboxyethoxy 1 ,4-benzoquinone, 2-methoxymethyl 1, 4-benzoquinone, 2-r-hydroxyethyl 1, 4-benzoquinone, 2-P-hydroxyethylthio 1,4-benzoquinone, 2, 5-bis-6-hydroxyethylthio 1, 4-benzoquinone, 2-3, Y-dihydroxypropylthio l,4-benzoquinone, 2-8-carboxyethylthio 1, 4-benzoquinone, 2-carboxymethyl l,4-benzoquinone, 2-1-hydroxyethylthio 6-methyl 1, 4-benzoquinone, 2-methoxycarbonyl 3-methoxy 1,4-benzoquinone, 2-methoxycarbonyl 1, 4-benzoquinone, 2-methylthio 1,4-benzoquinone, 2-dimethylamino 1, 4-benzoquinone, 2-acetylamino 5-methoxy 1,4-benzoquinone, 2-(B-hydroxyethylthio)methyl 1,4-benzoquinone, 2-(methylthio)methyl 1,4-benzoquinone, 4,5-dimethoxy 1,2-benzoquinone, 4-methyl 5-chloro 1,2-benzoquinone, 4,5-dimethyl 1,2-benzoquinone, 2,3-dimethyl 1,4-benzoquinone, 2-6-hydroxyethoxy 1,4-benzoquino,2, N-methylsulfonyl 1,4-benzoquinone monoimine, N-phenylsulfonyl 1,4-benzoquinone monoimine, 1,4-naphthoquinone, 1,2-naphthoquinone, 1,2-naphthoquinone 4-sulfonic acid, 2,3-dichloro 1,4-naphthoquinone, N-2,6-trichloro 1,4-benzoquinone imine.

In a first embodiment of the dyeing method using an oxidizing system, a composition containing, in an appropriate dye medium, at least one compound having formula in association with iodide ions is applied to the keratinous material, application of composition (A) being preceded or followed by application of a composition containing hydrogen peroxide in an appropriate dye medium.

This method can also be effected by applying to the keratinous fibers at least one composition containing the compound of formula in association with hydrogen peroxide in an appropriate dye medium, at a pH of between 2 and 7, preferably between 3.5 and 7, application of composition being preceded or followed by application of a composition containing iodide ions in an appropriate dye medium.

The iodide ion in this embodiment of the method is preferably selected from iodides of alkali metals, alkaline-earths or ammonium. More particularly, the iodide is potassium iodide.

The iodide ions are present in compositions or in proportions generally of between 0.007% and 4% by weight, preferably between 0.08% and 1.5% by weight expressed as the weight of I- ions with respect to the total weight of composition or In a second embodiment, the method can be effected using a nitrite as the oxidizing agent to develop the color. The following particularly preferred nitrites may be used in the present invention: nitrites of alkali metals, alkaline-earths or ammonium or of any other cosmetically acceptab.e cation when used to dye living human hair; organic nitrite derivatives such as, for example, amyl nitrite; nitrite vectors, i.e. compounds which form nitrites of the type defined above on transformation.

Particularly preferred nitrites are sodium, potassium or ammonium nitrites.

This embodiment of the method is carried out by applying composition based on formula defined above to the keratinous material, then an aqueous acid composition composition or containing at least one nitrite.

The nitrites are generally used in proportions of between 0.02 mole/liter and 1 mole/liter.

In accordance with a third embodiment of the method, the oxidizing agents are selected from hydrogen peroxide, chloramine T, chloramine B, periodic acid and its hydrosoluble salts, sodium hypochlorite, potassium ferricyanide, silver oxide, Fenton's reagent, lead (IV) oxide, cesium sulfate and ammonium persulfate. These agents ara preferably applied to the fibers in composition after application of composition These oxidizing agents are present in proportions which are sufficient to develop the color, preferably in proportions of between 0.004 mole and 0.7 mole, in particular between 0.01 mole and 0.04 mole per 100 g of composition.

In accordance with a fourth embodiment of the method, a composition is first applied to the keratinous fibers containing, in an appropriate dye medium, at a pH between 2 and 10, a metal anion having good affinity for keratin and an oxidoreduction potential which is greater than that of the compounds of formula This anion is preferably selected from permanganates or bichromates, more particularly potassium permanganate and sodium bichromate.

These metal anions are generally used at anionic molalities of greater than 10 3 mole/i 000 g, preferably up to 1 mole/i 000 g.

Next, a composition is applied containing a compound having formula as defined above, in an appropriate dye medium and a pH between 4 and Compositions containing the anions must not contain organic agents which could reduce the anions.

In accordance with a fifth embodiment of the invention, oxidation catalysts are used which are selected from metal salts such as salts of manganese, cobalt, iron, copper and silver.

By way of example, manganese sulfate, manganese lactate, cobalt chloride, ferric chloride, cupric chloride or ammoniacal silver nitrate can be used.

Preferred salts are copper salts. These salts are used in proportions of 0.01% to 2% expressed as the weight of metal ions with respect to the total weight of the composition containing the salts.

In this embodiment of the invention, the keratinous fibers, in particular hair, are placed in contact with a composition containing the metal salt in an appropriate dye medium, before or after application of composition containing the compound with formula rinsing being preferably carried out between the two steps.

The preferred embodiment of the invention consists in firstly applying a cupric salt and then composition containing the hydroxyindoline derivative with formula After rinsing, a solution of hydrogen peroxide may optionally be applied to lighten the color obtained.

In accordance with a sixth embodiment of the invention, rare earth salts are used. Rare earth salts which can be used in the method of the invention are selected from Lanthanide salts, in particular salts of cerium Ce 3 Ce 4 lanthanum La 3 europium Eu 2 Eu 3 gadolinium Gd 3 ytterbium Yb 2 Yb 3 and dysprosium Dy 3 Sulfates, chlorides and nitrates are preferred.

These rare earth salts are present in proportions of between 0.1% and 8% by weight with respect to the total composition weight.

Sulfates and c 'orides of cerium Ce 3 and Ce 4 are preferably used.

In accordance with a seventh embodiment of the invention, the composition containing the quinone derivative is applied before or after composition (A) containing the compound with formula 1,4-benzoquinone and 2-B-hydroxyethylthio 1,4benzoquinone are preferred quinone derivatives.

The concentration of quinone derivatives is preferably between 0.005 mole/liter and 1 mole/liter in composition The pH of composition is between 2 and 10, preferably less than 7.

When using hydrogen peroxide based compositions in the various methods described above, the hydrogen peroxide content is generally between 1 volume and volumes, preferably between 2 volumes and 10 volumes and more particularly between 3 volumes and 10 volumes.

The invention also relates to a dye means for keratinous fibers, in particular human keratinous fibers, comprising a plurality of components, for carrying out the dyeing method defined above and using an oxidizing system. In this case, the dye means comprise at least two components, of which a first is composition as defined above and containing the hydroxyindoline derivative with formula and the second is one of the compositions also a, defined above.

Components and respectively are selected from the various embodiments of the method described above.

The invention also relates to a device comprising a plurality of compartments, a "dye kit" or "dye outfit", comprising all the components for dyeing keratinous fibers in one or several successive applications with or without prior mixing as described above.

These devices are themselves known and may comprise a first compartment containing compositinn containing the hydroxyindoline derivative with formula in an appropriate dye medium and a second compartment containing composition as defined above and containing the oxidizing agent.

Devices containing a plurality of compartments for use in accordance with the invention may be equipped with means for mixing just before use and their contents may be packaged under an inert atmosphere.

When using an anhydrous medium containing the hydroxyindoline derivative with formula a third compartment may be provided containing an appropriate aqueous dye medium for mixing with the composition in the first compartment just before use.

The hydroxyindoline derivative with formula compositions and the method of the invention can be used to dye natural or colored hair which may or may not have been permed or straightened, or hair which has been heavily or lightly bleached and optionally permed.

They can also be used to dye fur or wool.

The following examples illustrate the invention without in any way limiting its scope.

PREPARATION EXAMPLE 1 SYNTHESIS OF 6-HYDROXY 7-METHOXYINDOLINE HYDROBROMIDE A) Synthesis of 6-benzyloxy 7-methoxyindoline

H

Using a spatula, 2.4 g of sodium borohydride was added to a cooled solution of 7 g of 6-benzyloxy 7-indole in 50 ml of dimethoxyethane under nitrogen. 12 ml of trifluoroacetic acid was added dropwise. After one hour at room temperature, 40 ml of 15% caustic soda was added before pouring into 200 ml of water. This was then extracted three times using 100 ml of ethyl acetate. The organic phases were mixed together, washed with water, dried and evaporated to dryness to produce 7 g of residue. The residue was chromatographed on silica using a heptane/ethyl acetate gradient (95/5 to 80/20). 3.1 g of a light yellow liquid was obtained which was used directly in the next step.

A single spot was observed in thin layer chromatography.

Rf 0.41 heptane/ethyl acetate 50/50.

B) Synthesis of 6-hydroxy 7-methoxyindoline hydrobromide HO H-Br 5 HO 3

OCH"

3 g of the indoline from example 1A) was suspended in 25 ml of 47% hydrobromic acid. After one hour of stirring at 40°C, this was diluted with 25 ml of deionized water then vacuum evaporated. The dark green residue was taken up into solution in water. 10 g of vegetable charcoal was added, followed by heating for 30 minutes on a boiling water bath. It was filtered over cellite and evaporated to dryness. The beige powder obtained was recrystallized from an ethanol/ethyl ether mixture. 1.6 g of beige crystals were obtained which had the following characteristics: Elemental analysis for C 9

H

12 BrNO 2 C H Br N 0 Calculated 43.92 4.91 32.47 5.69 13.00 Found 43.70 5.05 32.19 5.60 12.86 PREPARATION EXAMPLE 2 SYNTHESIS OF 6,7-DIHYDROXYINDOLINE

HYDROBROMID.

H-Br HO N 'H-r

H

g of 6-benzyloxy-7-methoxyindoline (example 1A) was mixed with 100 ml of 47% hydrobromic acid. The mixture was refluxed for one hour. After cooling, a precipitate was formed which was filtered then taken up into hot water. 10 g of vegetable charcoal was added and the mixture was left for 30 minutes on a boiling water bath. This was filtered over cellite and evaporated.

The solid obtained was washed with ethyl ether then acetone. The solid was redissolved in water then filtered and evaporated to give 3.4 g of a beige solid.

The proton NMR spectrum agreed with the expected structure.

EXAMPLE 1 COMPOSITION (A) 4-hydroxy hydrobromide 1 g Potassium iodide 0.8 g 960 ethyl alcohol 10 g Hydroxyethylcellulose sold by AQUALON under the trade name NATROSOL 250 HHR 1 g Glucoside alkylether sold at 60% AM by ROHM HAAS under the trade name TRITON CG 110 5 g AM Sodium laurylether sulfate 0.2 g AM Spot pH 4.9 Demineralized water qsp 100 g COMPOSITION (B) 12.5 volumes oxygenated water solution.

Composition was applied to permed gray hair and left for 15 minutes at room temperature. It was then rinsed and composition applied and left for 5 minutes. After rinsing and drying, the hair had been dyed dark golden iridescent blond.

EXAMPLE 2 COMPOSITION (A) 6-hydroxy 7-methoxyindoline hydrobromide 1 g Sodium laurylether sulfate oxyethylenated to 2 moles of ethylene oxide 15 g Ethyleneglycol monobutylether 10 g Demineralized water qsp 100 g Spot pH 3.1 COMPOSITION (B) Sodium periodate 5 g HC1 qs pH Demineralized water qsp 100 g Composition was applied to 90% white gray hair and left for 15 minutes. After rinsing, composition (B) was applied and left for 10 minutes.

The hair was rinsed and dried. It had been dyed a light natural ash blond.

EXAMPLE 3 6,7-dihydroxyindoline hydrobromide 96° ethyl alcohol Hydroxypropylcellulose sold by AQUALON under the trade name KLUCEL G 60% alkyl(Cg-Cl0)polyglucoside in buffered aqueous solution sold by ROHM HAAS under the trade name TRITON CG 110-60 Nonylphenol oxyethylenated to 9 moles of ethylene oxide Tartaric acid Triethanolamine pH 8.1 Demineralized water qsp 0.5 g 10 g 2 g 3.5 g 0.1 g 0.3 g 3.75 g 100 g The composition was applied to 90% white gray hair and left for 10 minutes. After rinsing and drying, the hair had been dyed light golden blond.

This color intensified during successive applications.

EXAMPLE 4 COMPOSITION (A) 4-hydroxy hydrobromide 1 g 960 ethyl alcohol 10 g Hydroxyethylcellulose sold by AQUALON under the trade name NATROSOL 250 HHR 1 g Glucoside alkylether sold at 60% AM by ROHM HAAS under the trade name TRITON CG 110 5 g AM Demineralized water qsp 100 g Spot pH 4.8 COMPOSITION (B) 20 volumes oxygenated water 66 ml 3.4% aqueous ammonia solution qsp 100 ml Composition was applied to permed gray hair and left for 10 minutes. After rinsing, composition was applied and left for 20 minutes. The hair was then rinsed and dried.

It had been dyed a matt light golden blond.

EXAMPLE COMPOSITION (A) 4,5-dihydroxyindoline hydrobromide 1 g 96' ethyl alcohol 10 g Propyleneglycol 2 g Nonylphenol oxyethylenated to 9 moles ethylene oxide 4 g Demineralized water qsp 100 g Spot pH 3.9 COMPOSITION (B) Sodium nitrite 2 g Demineralized water qsp 100 g HC1 qs pH 3.8 Composition was applied to 90% white gray hair and left for 20 minutes. After rinsing, composition (B) was applied and left for 5 minutes. The hair was then rinsed and dried. It had been dyed a matt golden ash blond.

EXAMPLE 6 COMPOSITION (A) Copper sulfate, 5H 2 0 Sodium laurylether sulfate oxyethylenated to 2 moles of ethylene oxide Hydroxyethylcellulose Monoethanolamine qs Demineralized water 1 g 15 g 2.4 g 100 g pH qsp COMPOSITION (B) 4,5-dihydroxyindoline hydrobromide 960 ethyl alcohol Sodium laurylether sulfate oxyethylenated to 2 moles of ethylene oxide Demineralized water qsp Spot pH 3.9 15 g 100 g Composition was applied to permed gray hair and left for 5 minutes. After rinsing, composition was applied and left for 10 minutes. The hair was rinsed and dried. It had been dyed a deep ash blue.

EXAMPLE 7 COMPOSITION (A) Cerium sulfate 1 g Demineralized water qsp 100 g Spot pH 1.6 COMPOSITION (B) 4,5-dihydroxyindoline hydrobromide i g Ethyleneglycol monobutylether 10 g Nonylphenol oxyethylenated to 9 moles of ethylene oxide 15 g Demineralized water qsp 100 g Spot pH Composition IA) was applied to permed gray hair and left for 10 minutes. It was rinsed and composition (B) was then applied and left for 10 minutes.

After rinsing and drying, the hair had been dyed a dark ash blond.

EXAMPLE 8 COMPOSITION (A) 5-methoxy 6-hydroxyindoline hydrobromide 2 g 960 ethyl alcohol 8 g Demineralized water qsp 100 g Spot pH COMPOSITION (B) Sodium chlorite 4 g Demineralized water qsp 100 g Spot pH 10.1 Just before use, composition and composition were mixed in equal weights. The mixture was applied to 90% white gray hair and left for 20 minutes. After rinsing and drying, the hair had been dyed a dark ash blond.

Claims (21)

1. Use in dyeing keratinous fibers, in particular human keratinous fibers, of a hydroxyindoline derivative having formula: HO CH 2 R 2 0 N 2 R, where: R 1 represents a hydrogen atom or a C 1 -C 4 alkyl group; R 2 represents a hydrogen atom or a C 1 -C 4 alkyl group; the OH and -OR 2 groups are in the 4, 5, 6 or 7 position on the benzene ring, provided that, when in the 5 and 6 positions, R 2 represents a C 1 -C 4 alkyl group; and acid addition salts of these compounds.

2. Use according to claim 1 characterized in that the salts are selected from hydrochlorides or hydrobromides.

3. Use of 7-methoxy 6-hydroxyindoline, 6,7-dihydroxyindoline, 5-hydroxy 4-methoxyindoline, 4,5-dihydroxyindoline, 5-methoxy 6-hydroxyindoline,

7-hydroxy 6-methoxyindoline, 7-methoxy 4-hydroxyindoline, 4-hydroxy 5-methoxyindoline, 5-hydroxy 6-methoxyindoline, and 4,7-dihydroxyindoline or their acid addition salts in dyeing keratinous fibers. 4. Dye composition for use in dyeing keratinous fibers characterized in that it contains at least one hydroxyindoline derivative with formula as defined in any one of claims 1 to 3 in an appropriate dye medium. Composition according to claim 4 characterized in that the hydroxyindoline derivative with formula (I) is present in the composition in proportions of between 0.01% and 8% by weight with respect to the total composition weight, preferably between 0.03% and 5% by weight. 6. Composition according to claim 4 or claim characterized in that the appropriate dye medium is an aqueous medium constituted by water or a water/solvent mixture. 7. Composition according to claim 6 characterized in that the solvents are selected from ethyl alcohol, propyl or isopropyl alcohol, tertiobutyl alcohol, ethyleneglycol, monomethyl, monoethyl and monobutyl ethers of ethyleneglycol, ethyleneglycol monoethylether acetate, propyleneglycol, propyleneglycol and dipropyleneglycol monomethylethers and methyl lactate.

8. Composition according to any one of claims 4 to 7 characterized in that the composition contains fatty \mides, anionic, cationic, non-ionic or amphoteric surfactants or mixtures thereof, thickening agents, perfumes, sequestrating agents, film-forming agents, treatment agents, dispersing agents, packaging agents, preservatives, opacifiers and keratinous fiber swelling agents or mixtures thereof.

9. Composition according to any one of claims 4 to 8 characterized in that the pH of the composition is between 3 and 12. Method of dyeing keratinous fibers, in particular human keratinous fibers, characterized in that at least one composition as defined in any one of claims 4 to 9 is applied to the fibers and left in contact with the fibers for a period of time sufficient to develop a color, either in air or using an oxidizing system, followed by rinsing.

11. Method according to claim 10 characterized in that the color is allowed to develop in contact with air without the addition of an external oxidizing agent.

12. Method according to claim 10 characterized in that composition containing at least one hydroxyindoline derivative with formula as defined in any one of claims 1 to 3 is applied to the fibers in an appropriate dye medium, the color being developed using a chemical oxidizing system constituted by: iodide ions and hydrogen peroxide, composition containing in addition, either iodide ions or (b) hydrogen peroxide, and application of composition is preceded or followed by application of composition (B) containing, in an appropriate dye medium, either: hydrogen peroxide at a pH of between 2 and 12, when composition contains iodide ions, or: iodide ions at a pH of between 3 and 11 when composition contains hydrogen peroxide; (ii) nitrites, application of composition being followed by application of an aqueous composition (B) having an acidic pH, composition or composition (B) containing at least one nitrite; (iii) oxidizing agents selected from hydrogen peroxide, periodic acid and its hydrosoluble salts, sodium hypochlorite, chloramine T, chloramine B, potassium ferricyanide, silver oxide, Fenton's reagent, lead (IV) oxide, cesium sulfate, ammonium persulfate and alkaline chlorites; these oxidizing agents being present in composition containing the hydroxyindoline derivative with formula or applied simultaneously or sequentially by means of a composition containing them in an appropriate dye medium; (iv) metal anions selected from permanganates or bichromates, the oxidizing agents being applied by means of an aqueous composition at a pH of 2 to 10, before application of composition salts of metals from groups 3 to 8 of the periodic table, these metal salts being applied by means of a composition containing them in an appropriate dye medium, compositicn being applied before or after application of composition (vi) rare earth salts applied by means of a composition containing them in an appropriate dye medium, composition being applied before or after application of composition containing the hydroxyindoline derivative with formula (vii) a quinone derivative selected from ortho- or parabenzoquinones, ortho- or parabenzoquinone monoimines or diimines, 1,2- or 1,4-naphthoquinones, ortho- or parabenzoquinones sulfonimides, a,w-alkylene-bis- 1,4-benzoquinones or 1,2- or 1,4-naphthoquinone monoimines or diimines by means of a composition (B) containing them in an appropriate dye medium, the hydroxyindoline derivative with formula and quinone derivatives being selected so that the difference in oxidcreduction potential AE between the oxidoreduction potential Ei of the hydroxyindoline derivative with formula determined voltametrically at pH 7 in a phosphate medium on a vitreous carbon electrode and the oxidoreduction potential Eq of the quinone derivative determined polarographically at pH 7 in a phosphate medium on a mercury electrode with reference to a saturated calomel electrode is such that: AE Ei Eq 320 millivolts; composition being applied either before or after application of composition containing the hydroxyindoline derivative with formula

13. Method according to claim 12 characterized in that a composition containing in an appropriate dye medium at least one hydroxyindoline derivative with formula in association with iodide ions is applied to the keratinous material, application of composition (A) being preceded or followed by application of a composition containing hydrogen peroxide in an appropriate dye medium.

14. Method according to claim 12, characterized in that at least one composition containing a hydroxyindoline derivative with formula in association with hydrogen peroxide in an appropriate dye medium at a pH of between 2 and 7 is applied to the keratinous fibers, application of composition being preceded or followed by application of a composition (B) containing iodide ions in an appropriate dye medium. Method according to claim 13 or claim 14 characterized in that the iodide ions are present in composition or in proportions of between 0.007% and 4% by weight expressed as I- ions with respect to the total weight of composition or

16. Method according to claim 12, characterized in that a composition containing the hydroxyindoline derivative with formula is applied to the keratinous material followed by application of an aqueous acidic composition composition or composition (B) containing at least one nitrite selected from nitrites of alkali metals, alkaline-earths or ammonium or any other cosmetically acceptable cation, an organic nitrite derivative and nitrite vectors generating a nitrite of the type defined above, the nitrites being present in proportions of between 0.02 mole/liter and 1 mole/liter.

17. Method according to claim 12 characterized in that a composition containing a metal anion with a good affinity for keratin selected from permanganates or bichromates is applied in an appropriate dye medium at a pH of between 2 and 10 to the keratinous fibers followed by application of a composition containing a hydroxyindoline derivative with formula in an appropriate dye medium at a pH of between 4 and 10, the permanganates or bichromates being used in anion molalities greater than 10 3 mole/i 000 g, preferably up to 1 mole/i 000 g and in that the compositions do not contain any organic agent which would reduce the anions.

18. Method according to claim 12 characterized in that a composition containing a hydroxyindoline derivative with formula is applied in an appropriate dye medium to the keratinous fibers before or after which a composition is applied containing a metal salt selected from manganese, cobalt, iron, copper and silver salto in an appropriate dye medium, the metal salts being used in proportions of between 0.01% and 2% by weight expressed as the weight of metal ions with respect to the total composition weight.

19. Method according to claim 12 characterized in that a composition containing a hydroxyindoline derivative with formula is applied in an appropriate dye medium and a composition containing a rare earth salt selected from cerium, lanthanum, europium, gadolinium, ytterbium and dysprosium in an appropriate dye medium is applied before or after application of composition the rare earth salts being present in proportions of between 0.1% and 8% by weight with respect to the total composition weight.

20. Method according to claim 12, characterized in that a composition containing at least one hydroxyindoline derivative with formula is applied in an appropriate dye medium and a composition (B) containing a quinone derivative selected from 1,4-benzo- quinone and 2-6-hydroxyethylthio 1,4-benzoquinone in an appropriate dye medium is applied before or after application of composition the quinone derivative being present in proportions of between 0.005 mole/liter and 1 mole/liter.

21. Method according to claims 12 to characterized in that when a hydrogen peroxide based oxidizing means is used the hydrogen peroxide content of the oxidizing means is between 1 volume and 40 volumes, preferably between 2 volumes and 10 volumes.

22. Dye means for keratinous fibers, in particular human keratinoas fibers, comprising a plurality of components, characterized in that it comprises a first component constitated by a composition containing a hydroxyindoline derivative with formula as defined in any one of claims 12 to 20 and a second component constituted by a composition as defined in any one of claims 12 to 21.

23. Device comprising a plurality of compartments or "dye kit" characterized in that the various compartments contain the various components of the dye means defined in claim 22.

24. Compounds constituted by the hydrobromides of hydroxyindoline derivatives having formula as defined in any one of claims 1 to 3.

25. 6-hydroxy 7-methoxyindoline and its acid addition salts.

26. 6,7-dihydroxyindoline and its acid addition salts. Title: HYDROXYINDOLINE DERIVATIVE BASED DYE COMPOSITIONS The invention relates to the use in dyeing keratinous material, in particular human keratinous material, of a hydroxyindoline derivative having formula where: R 1 represents hydrogen or a C 1 -C 4 alkyl group; R 2 represents hydrogen or a C 1 -C 4 alkyl group; OH and -OR 2 are in the 4, 5, 6 or 7 positions provided that, when in the 5 and 6 positions, R 2 is an alkyl group; and to their acid addition salts. INTERNATIONAL SEARCH IREPORT International application No. PCT/FR 92/00856 A. CLASSIFICATION OF SUBJECT MATTER C07D209/08; A61K7/13 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) C07D; A61K Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. P,X WO, A, 9 117 739 (HENKEL) 1-23 28 November 1991 see the whole document Y FR, A, 2 636 237 (OREAL) 1-26 16 March 1990 see claims 1-26; examples Y DE, A, 1 916 139 (OREAL) 1-26 27 November 1969 see claims 1-8; examples FR, A, 2 008 797 cited in the application A GB, A, 2 187 456 (OREAL) 1-26 9 September 1987 see the whole document Further documents are listed in the continuation of Box C. O See patent family annex. Special categories of cited documents: later document published after the international filing dateor priority date and not in conflict wilh the application but cited to understand document defining the general state of the art which is not considered the principle or theory underlying the invention to be of particular relevance earlier document but published on or after the international filing date document of particular relevance; the claimed invention cannot be considered novel or cannot be considered to involve an inventive document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other special reason (as specified) document of particular relevance; the claimed invention cannot be document referring to an oral disclosure, use, exhibition or other considered to involve an inventive step when the document is means combined with oneor more other such documents, such combination means being obvious to a person skilled in the art document published prior to the international filing date but later than the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report November 1992 (20.11.92) 14 December 1992 (14.12.92) Name and mailing address of the ISA/ Authorized officer EUROPEAN PATENT OFFICE Facsimile No. Telephone No. Form PCT/ISA/210 (second sheet) (July 1992) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION No. FR 9200856 SA 64788 This mimex lists the patent family members mciating to the patent documents cited in the above-maintioned ntrational march report. The memibers ame as contained in the European Patent Office EDP file on The European Patent Office is in ao way liable for these particulars which are merely given for the purpose of information. 20/ 11/92 Patent document -F Publication Patent family I Publication cited in search rMort dat member(s) -F dat WO-A-9117739 28-11-91 OE-A- 401617 7 21-11-91 FR-A-2636237 16-03-90 LU-A- 87338 06-04-90 BE-A- 1002259 06-1 190 CH-A- 679552 13-04-92 GB-A,B 2224754 16-05-90 JP-A- 2115163 27-04-90 US-A- 5131911 21-07-92 DE-A-1916139 27-11-69 BE-A- 732421 03-11-69 FR-A- 2008797 23-01-70 GB-A- 1217479 31-12-70 LU-A- 56102 14-01-70 GB-A-2187456 09-09-87 LU-A- 86346 11-11-87 BE-A- 1000139 26-04-88 CH-A- 674802 31-07-90 DE-A- 3707088 10-09-87 FR-A,B 2595245 11-09-87 JP-A- 62270663 25-11-87 NL-A- 8700547 01-10-87 SE-A- 8700909 07-09-87 US-A- 4822375 18-04-89 bi For more details about this annex: se official Journal of the European Patent Office, No. 12tB2