AU652346B2 - Methods for dyeing keratinous fibres with aminoindoles, compositions and devices for use - Google Patents

Abstract

Process for dyeing keratinous fibres, especially human keratinous fibres such as the hair, wherein there is applied on these fibres a composition (A) containing, in a medium suitable for dyeing, at least one aminoindole corresponding to the formula: <IMAGE> in which: R1 and R3, independently of one another, represent a hydrogen atom or a C1-C4 alkyl group; R2 denotes hydrogen or a C1-C4 alkyl group or a group COOR', R' being a hydrogen atom or a C1-C4 alkyl group; R4 represents a hydrogen atom or a C1-C4 alkyl, C1-C4 hydroxyalkyl or C2-C4 polyhydroxyalkyl group; Z1 represents a hydrogen or halogen atom, an alkyl group or a group OR; R being a hydrogen atom or a C1-C4 alkyl group; Z2 represents a hydrogen atom or a C1-C4 alkyl group; and its salts the colour being developed using an oxidising system.

Description

COMMONWEALQ4Fr ITR 2 3 46 Form PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification LogcQd: Accepted: Published: SPriority S Related Art: Name of Applicant

L'OREAL

Address of Applicant "Actual Inventor Address for Service 14, rue Royale F-75008 Paris, France GERARD LANG, ALEX JUNINO and JEAN COTTERET WATERMARK PATENT TRADEMARK ATTORNEYS.

LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTRALIA Complete Specification for the invention entitled: METHODS FOR DYEING KERATINOUS FIBRES WITH AMINOINDOLES, COMPOSITIONS AND DEVICES FOR USE The following statement is a full description of this invention, including the best method of performing it known to us 1 Methods for dyeing keratinous fibres with aminoindoles, compositions and devices for use.

The present invention relates to new methods for dyeing keratinous fibres and in particular human keratinous fibres, such as hair, using an aminoindole, and to tinctorial compositions and to devices enabling these methods to be used.

The dyes of the indole family and in particular 5,6-dihydroxyindole and its derivatives are well known for their use in dyeing keratinous fibres and in particular human hair.

French Patents FR-A-1 133 594, 1 166 172 and 2 390 158 propose methods for dyeing with the aid of 5,6dihydroxyindole, using metal cations playing the role of 15 melanogenesis promoter.

5,6-Dihydroxyindole leads in particular to black or more or less grey hues.

0o0 Various dyeing methods using indole derivatives in combination with oxidizing systems, such as inorganic 20 anions, such as, for example, iodide, or metal anions, such as permanganate or bichromate, have also been described in FR-A-2 593 061, 2 593 062 and 2 594 331.

The inventors have just discovered that a particular category of indoles substituted on the aromatic ring by an amine function enabled particularly valuable use and powerful hues to be obtained when the dyeing is developed by oxidizing agents.

The invention therefore relates to a method for dyeing keratinous fibres and in particular human kera- 30 tinous fibres using aminoindoles in combination with an oxidizing system.

The invention also relates to the tinctorial compositions used in the course of this method, as well as to the device intended to be used in carrying out this method.

Further subjects of the invention will become apparent on reading the description and the examples which follow.

2 The method for dyeing keratinous fibres, and in particular human keratinous fibres such as hair, according to the invention, is essentially characterized in that a composition containing, in a medium appropriate for dyeing, at least one aminoindole corresponding to the formula: 2 R3

(I)

R4NH R1 in which: RI and R 3 independently of one another, represent 10 a hydrogen atom or a C 1

-C

4 alkyl group;

R

2 denotes hydrogen or a C 1

-C

4 alkyl group or COOR', R' being a hydrogen atom or a C 1

-C

4 alkyl group;

R

4 represents a hydrogen atom or a C 1

-C

4 alkyl, Ci-C 4 hydroxyalkyl or C 2

-C

4 polyhydroxyalkyl group; 15 Zi represents a hydrogen or halogen atom or a Cl-C 4 alkyl group or OR; R being a hydrogen atom or a C 1

-C

4 alkyl group; and

Z

2 represents a hydrogen atom or a Ci-C 4 alkyl group; and its salts is applied to said fibres, the colour being developed with the aid of an oxidizing system consisting 0 of: iodide ions and hydrogen peroxide, the composition in this case also containing either (a) iodide ions or hydrogen peroxide and the application of the composition being preceded or followed by the application of a composition which contains, in a medium appropriate for dyeing, either: hydrogen peroxide at a pH of between 2 and 12 and preferably between 2 and 7, when the composition (A) contains iodide ions, or iodide ions at a pH of between 3 and 11, when the composition contains hydrogen peroxide; (ii) nitrites, the application of the composition being followed by the application of an aqueous composition having an acid pH, the composition or the composition containing at least one nitrite; (iii) oxidizing agents chosen from periodic acid and its water-soluble salts, sodium hypochlorite, potassium ferricyanide, silver oxide, Fenton's reagent, lead(IV) oxide, caesium sulphate and ammonium persulphate, these oxidizing agents being present in the composition or being applied separately; at the same time or subsequently, by means of a composition (B) containing them in a medium appropriate for dyeing; (iv) metal anions chosen from the permanganates or bichromates, these oxidizing agents being applied by means of an aqueous composition having a pH of from 2 to 10, before the application of the composition salts of metals of groups III to VIII of the 20 periodic table, these metal salts being applied in a separate step by me 'ns of a composition containing these salts in a medium appropriate for dyeing; (vi) rare earth salts, these rare earth salts being applied by means of a composition containing *25 them in a medium appropriate for dyeing, the composition being applied before or after the application of the

C

composition According to the invention, the application of e the compositions and is preferably separated by a rinsing.

Amongst the aminoindole derivatives corresponding to the formula the following may be mentioned: 4aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5-amino-6-methoxy-2,3-dimethylindole, 2,3-dimethylindole, 5-amino-6-hydroxy-2,3-dimethylindole, 5-hydroxy-6-amino-2,3-dimethylindole, 6-N-p-hydroxyethylaminoindole, 6-N-p-hydroxyethylamino-l-methylindole, 6methylaminoindole, (5 or 6)-amino-N-methylindole, 2carboxy-6-aminoindole, 4-amino-2,3-dimethylindole, -4 6-amino-2, 3-dimethylindole, 7-amino-2, 3-dimethylindole, 6 -amino- 3-ethyl-2 -methyl indole, 6 -amino- 3-methylindole, 6-amino-2-methylindole, 6-alino-2-ethoxycarbony'lindole and 7 -amino- 3-ethyl- 2-methylindole, 6-N- y-dihydroxypropyl)aminoindole, 2,3,4, 5-tetramethyl-6-aminoindole, 2, 3-dimethyl-5-chloro-6-aininoindole, 2, ethyl-6-aminoindole, 2, 3,4-trimethyl-6-aminoindole, 2-methyl-5-hydroxy-6'-,Ai~inoindole, 4-methylaminoindole, 4-amino-l-methylindoie, 2, 3-dimethyl-6-aminoindole, 2,3,7-trimethyl-6-aminoindole, 2, 3, 5-trimethyl- 6-aminoindole and their salts.

The new compounds belonging to the formula (I) correspond to the formula (IA): H3(IA) in which: RH alky R 4 denotes hydrogen, C 1

-C

4 alkyl, C 1

-C

4 hydroxyaklor C.-C 4 polyhydroxyalkyl; Z, denotes hydrogen, alkyl or halogen; and

Z

2 denotes hydrogen or Cl-C 4 alkyl.

provided that at least one of -the radicals Z, 9 or Z 2 is other than hydrogen.

9.9...Amongst the new compounds, the following may be mentioned in particular: 2,3 ,7-trixnethyl-6-axninoindole, 5-tetramethyl-6-aminoindole, 2, 3 -dimethyl- 5-ethyl 6-aminoindole, 2,3-dimethyl-5-chloro-6-aminoindole and 2,3, 4-trimethyl-6-aninoindole.

The compounds of f ormula (IA) in which R 4 denotes hydrogen are prepared in accordance with the following reaction scheme: 2 Redctiton CH3C0O1N-' NH2 *000 0 so a 0 *0S*0 Deac'~tylation (I ID) 1st sten: It consists in an acetylation of the inonosubstituted or disubstituted reta-nitroaniline of formula (IIA). The reaction concerned is a conventional acetylation using acetic anhydride in a solvent, such as ethyl acetate, ref luxing the solvent.

2nd step: The acetylated compound (IIB) is reduced in accordance with the conventional procedures. This reduction is effected either by iron/acetic acid in water at a temperature varying between 500 and 95*C or by hydrogen transfer using, as catalyst, Pd/C in the presence of cyclohexane, in a solvent at a temperature between ambient temperature and the ref lux temperature of the 6 solvent (solvents which may be mentioned are lower C 1

-C

4 alcohols), or by catalytic hydrogenation using Pd/C or Raney nickel as catalyst.

3rd step: The compound (IIC) is subjected to a condensation reaction with 3-bromobutan-2-one in dimethylformamide at a temperature between ambient temperature and 120"C.

4th step: The compound (IID) is deacetylated in the presence of hot concentrated hydrochloric acid. The compounds (II) are thus obtained.

The compound (IA) in which R 4 is other than hydrogen is obtained from the compound (II) (R 4 H) by the methods for substitution of aromatic amines, in accordance with the reaction scheme: *2 2 X Z4 i 2 *H3 tosylation 3 Zor Z I- H3 formylation NH CH3 H2 p Compound( Ii) (IA) 4 S.X-R4 /(X=halogan 2 zii 3 7 H3 Compound (IA) Rz

(P'H)

The compound (IIA) is obtained by formylation or tosylation. The compound (IIA) is subsequently alkylated .il: 7 by means of an alkyl halide X-R 4 When the alkyl halide is used in excess, a second group R 4 is introduced. The product (IA) is obtained by deformylation or detosylation of the compound (IIB).

Amongst the hydroxylation method, those which may be mentioned are the action of f-chloroethyl chloroformate on the compound which enables the corresponding p-chloroethyl carbamate to be obtained initially, which compound is subsequently subjected to the action of a strong inorganic base, enabling the compound (IA) for vAich the radical R 4 is a p-hydroxyethyl radical to be obtained.

According to a first variant of the invention, a composition containing, in a medium appropriate for dyeing, at least one dye of formula in combination with iodide ions is applied to the keratinous materials, the application of the composition being preceded or followed by the application of a composition (1L) which contains hydrogen peroxide in a medium appropriate for 20 dyeing.

This riothod can also be carried out by applying to the keratinous fibres at least one composition (A) containing, in a medium appropriate for dyeing, the dye of formula in combination with hydrogen peroxide, 25 having a pH of between 2 and 7 and preferably between and 7, the application of the composition being preceded or followed by the application of a composition which contains iodide ions, in a medium appropriate :for dyeing.

The iodide ion in this variant of the method according to the invention is preferably chosen from alkali metal iodides, alkaline earth metal iodides or ammonium iodide and more particularly consists of potassium iodide.

The iodide ions are present in the compositions or in proportions of generally between 0.007 and 4% by weight, expressed as I- ions, and preferably between 0.08 and 1.5% by weight relative to the total weight of the composition or 8 According to a second variant of the invention, the method can be carried out using a nitrite as oxidizing agent to develop the colouring. The nitrites more particularly usable according to the invention are: alkali metal nitrites, alkaline earth metal nitrites or ammonium nitrite or nitrites of any other cation which is cosmetically acceptable when it is used for dyeing living human hair; organic derivatives of nitrites, such as, for example, amyl nitrite; nitrite carriers, that is to say compounds which by conversion give rise to a nitrite of the type defined above.

The particularly preferred nitrites are sodium nitrite, potassium nitrite or ammonium nitrite.

This variant of the method is carried out by applying to the keratinous materials the composition (A) e based on the dye of formula defined above and then an aqueous acid composition the composition or (B) 20 containing at least one nitrite.

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

According to a third variant of the invention, the oxidizing agents chosen from periodic acid and its water-soluble salts, sodium hypochlorite, potassium ferricyanide, silver oxide, Fenton's reagent, leadjIV) oxide, caesium sulphate and ammonium persulphate a.e preferably applied to the fibres by means of a composition and after the application of the composition The particularly preferred oxidizing agents of this group are periodic acid and its water-soluble salts, such as the lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, manganese, iron, copper, zinc and aluminium salts, the sodium and potassium salts being particularly preferred.

These oxidizing agents are present in proportions sufficient to develop a colouring, preferably between 0.004 mole and 0.07 mole and in particular between 9 0.01 mole and 0.04 mole per 100 g of composition.

According to a fourth var" .c of the invention, a composition containing, in a medium appropriate for dyeing, at a pH of between 2 and 10, an anion of a metal having a good affinity for keratin and having an oxidationreduction potential higher than that of the compounds of formula is initially applied to the keratinous fibres. This anion is preferably chosen from the permanganates or the bichromates and more particularly potassium permanganate and sodium bichromate.

Subsequently a composition containing, in a medium appropriate for dyeing, at a pH between 4 and a dye corresponding to the formula defined above is applied.

These metal anions are generally used in molar amounts of anions of more than 10 3 inoles/1,000 g up to preferably 1 mole/l,000 g. The compositions containing the anions must not contain organic agents having a* reducing effect thereon.

20 According to a fifth variant of the invention, oxidation catalysts are used chosen from metal salts, such as manganese, cobalt, iron, copper and silver salts.

Manganese sulphate, manganese lactate, cobalt chloride, ferric chloride, cupric, chloride and ammoniacal silver nitrate may be mentioned by way of example. The preferred salts -are the copper salts. These salts are used in proportions of 0.01 to expressed as metal ion.

According to this va 'ant, the keratinous fibres, •and in particular the hair, aL (is) brought into contact with a composition containing the metal salt in a medium appropriate for dyeing, before or after the application of the composition containing the compound of formula and rinsing is preferably carried out between the two steps.

The preferred embodiment consists in applying a cupric salt initially and the composition subsequently.

This dyeing may be followed, after rinsing, by the application of a solution of hydrogen peroxide to 10 lighten the colour obtained if necessary.

According to a sixth variant, rare earth salts are used. The rare earth salts which can be used according to the invention are chosen from the salts of lanthanides, and in particular the cerium Ce 3 and Ce 4 lanthanum La 3 europium Eu 2 and Eu 3 gadolinium Gd 3 ytterbium Yb 2 and Yb 3 and dysprosium Dy 3 salts. The preferred salts are, in particular, the sulphates, chlorides or nitrates.

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

Cerium Ce 3 and Ce4+ salts in the form of sulphates and chlorides are preferably used.

When compositions based on hydrogen peroxide are used, the hydrogen peroxide content is generally between 1 and 40 volumes and preferably between 2 and 10 volumes and more particularly between 3 and 10 volumes.

According to another embodiment, a tinctorial 20 composition containing, in a cosmetically acceptable aqueous medium having a pH of less than or equal to 7, at least one indole derivative corresponding to the formula: R4 2 I |(II) in which:

R

1 and R 2 which may be identical or different, denote H or CH 3

R

3 denotes H, NH z OH or -OCH 3

**R

4 denotes H, NH 2 OH or -OC 2

H

s R denotes H, NH 2 OH or -NHCH 2

CH

2 OH; and R, denotes H or OH; at least two of the radicals R 3

R

4 Rs and R 6 denoting hydrogen, and at least one and one only of the groups R 3

R

4 or Rs denoting NH 2 or -NHCH 2 CH20H for Rs; and when R 5 denotes an amino group and R 4 a, OH group, R, and R z denote CH 3 11 and the salts of corresponding acids, is applied initially.

After an exposure time followed by rinsing and drying, an alkaline oxidizing solution is subsequently applied, this application being followed by rinsing and shampooing.

The Applicant has found that this method enabled varied hues having glints or natural light to dark blond, copper and dark auburn hues to be obtained which were uniform even after several superpositions and covered the hair well.

The more particularly preferred dyes in this embodiment are chosen from 4-aminoindole, aminoindole, 6-aminoindole, 6-amino-2,3-dimethyl-5-hydroxyindole and 6-p-hydroxyethylaminoindole.

The amount of aminoindoles corresponding to the am formula used in the composition according to the invention, is generally in proportions of between 0.01 and 5% by weight relative to the total weight of the "20 composition, and preferably between 0.03 and 2.5% by weight.

The compositions which can be used according to the invention can be in various forms, such as in the form of lotions, thickened to a greater or lesser extent, 25 creams, foams and gels. These compositions may also be provided in multi-compartment devices or kits containing the various components intended to be mixed at the time of use, or in the form of aerosols.

The compositions which can be used in the method according to the invention and which are also a subject of the invention are characterized in that they contain, in a medium appropriate for dyeing, at least one aminoindole derivative of formula and at least iodide ions or nitrites, as defined above.

The proportions of the various constituents are as defined above.

The medium appropriate for dyeing is preferably an aqueous medium which must be cosmetically acceptable when the compositions .are intended for dyeing living 12 human hair. This aqueous medium can consist of water or of a water/solvent(s) mixture.

The solvents are chosen from the organic solvents and preferentially from ethyl alcohol, propyl alcohol or isopropyl alcohol, tertiary butyl alcohol, ethylene glycol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, ethylene glycol monoethyl ether-acetate, propylene glycol, propylene glycol and dipropylene glycol monomethyl ethers, and methyl lactate.

The particularly preferred solvents are ethyl alcohol, propylene glycol and ethylene glycol monobutyl ether.

According to another embodiment, the medium appropriate for dyeing can consist of anhydrous solvents, such as those defined preferentially above, the composition in this case being either mixed at the time of use with an aqueous medium or applied to the keratinous fibres previously wetted with an aqueous composition.

According to the invention, a medium containing less than 20 1% of water is termed an anhydrous solvent medium.

When the medium appropriate for dyeing is aqueous, the pH of the composition is preferably between 2 and 7 and in particular between 3.5 and 7.

When the medium appropriate for dyeing consists a water/solvent(s) mixture, the solvents are used in concentrations of between 0.5 and 75% by weight, relative to the total weight of the composition, preferably between 2 and 50% and more particularly between 2 and .by weight.

In addition to the indole dye corresponding to the formula or (II) above, the colouring composition can contain other indoles, amongst which 2-methyl-5,6- S* dihydroxyindole and its corresponding acid addition salt, 5,6-dihydroxyindole and 5,6-dihydroxy-2-carboxyindole may be mentioned.

The compositions according to the invention may contain any other adjuvants customarily used for dyeing kerat'.nous fibres and in particular cosmetically acceptable adjuvants, to the extent that these compositions are 13 are applied for dyeing living human hair.

In this latter case, the compositions may contain, in particular, fatty amides in preferential proportions of 0.05 to 10% by weight, anionic, cationic, nonionic or amphoteric surfactants or their mixtures, preferably present in proportions of between 0.1 and by weight, thickeners, perfumes, sequestering agents, film-forming agents, treatment agents, dispersing agents, conditioning agents, preservatives, opacifying agents and swelling agents for keratinous fibres.

The thickeners are chosen from sodium alginate, gum arabic, guar gum, heterobiopolysaccharides, such as xanthan gum, scleroglucans, cellulose derivatives, such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and the sodium salt of carboxymethylcellulose and preferentially crosslinked acrylic acid polymers.

Inorganic thickeners may also be used, such as bentonite. These thickeners are used on their own or as 20 a mixture and are preferably present in proportions of between 0.1 and 5% by weight relative to the total weight of the composition, and advantageously between 0.5 and 3% by weight.

The alkalinising agents which may be used in the 25 compositions can be, in particular, amines, such as alkanolamines, alkylamines, alkali metal hydroxides or carbonates or ammonium hydroxide or carbonate.

The acidifying agents which may be used in these .compositions may be chosen from lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid and citric acid.

It is, of course, possible to use any other acceptable alkalinizing or acidifying agent, in particular in the case of cosmetic dyeing of the hair.

When the compositions are used in the form of foam, they may be packaged under pressure and in an aerosol device in the presence of a propellant and at least one foam generator.

The foam generators may be anionic, cationic, 14 nonionic or amphoteric foaming polymers, or their mixtures, or surfactants of the type of those defined above.

In the embodiment using the dyes of formula (II), the oxidizing composition preferably consists of an aqueous solution of oxidizing agent which is mixed at the time of use with an alkaline aqueous solution which may contain solvents and surfactants.

The oxidizing agent is chosen from hydrogen peroxide, urea peroxide and per salts such as alkali metal or ammonium percarbonates and perborates.

The alkaline agents are chosen from ammonia and alkanolamines such as 2-amino-2-methylpropan-l-ol, monoethanolamine, monomethylethanolamine or dimethylethanolamine.

The aqueous solution of oxidizing agent can contain solvents of the type defined above, surfactants and also self-emulsifiable waxes or polyoxyethylenated alcohols for thickening these solutions.

The proportion of oxidizing agent in the composi- 20 tions is between 1 and 15% by weight relative to the total weight of the oxidizing composition, and preferably between 1 and 8%.

The proportion of oxidizing agent in the alkaline oxidizing compositions which are applied to the hair is *.25 between 1 and 10% by weight relative to the total weight of the composition, and preferably between 1 and The pH of the oxidizing composition is between 8.5 and 12.

The invention also relates to an agent for dyeing keratinous fibres and in particular human keratinous fibres, containing several components, one of which components consists of the composition defined above and the other component consists of one of the compositions also defined above, the respective components being chosen in accordance with the various variants described above.

Another subject of the invention is a multicompartment device also termed "dyeing kit" or "dyeing set" comprising all the components intended to be applied 15 to the keratinous fibres for a given dyeing, in successive applications with or without premixing, as mentioned above.

Devices of this type are known per se and can comprise a first compartment containing the composition comprising the aminoindole derivative of formula (I) in a medium appropriate for dyeing, and, in a second compartment, a composition defined above.

When the medium containing the aminoindole derivative of formula is anhydrous, a third compartment can be provided containing an aqueous medium appropriate for dyeing and intended to be mixed before use with the composition in said first compartment.

The multicompartment devices which can be used according to the invention can be fitted with means of mixing at the time of use and their contents can be ,0 packaged under an inert atmosphere.

The method and the compositions used, according to the invention, can be employed for dyeing natural or 20 already dyed hair which may or may not have been given a permrnent wave or may or may not have been straightened, or strongly or slightly bleached hair, which may have been given a permanent wave. It is also possible to use them for dyeing fur or wool.

*25 The examples which follow are intended to illustrate the invention without any restriction being implied.

PREPARATION EXAMPLE 1 Preparation of 6-N-B-hvdroxvethylaminoindole 30 Step 1 Preparation of 6-N- (-chloroethoxycarbonyl)aminoindole 0.05 mol (6.6 g) of 6-aminoindole and 5.5 g of calcium carbonate in 30 ml of dioxane are heated to reflux. 0.055 mol (7.9 g) of p-chloroethyl chloroformate is added little by little. The reaction mixture is diluted with The expected product precipitates. It melts at 134°C.

Analysis of the product recrystallized from ethanol gives the following results: 16 Analysis for CjjHjjN 2 0 2 Cl C H Cl O N Calculated 55.36 4.65 14.85 13.41 11.74 Found 55.40 4.68 14.72 13.27 11.67 Step 2 Preparation of 6-N-8-hvdroxyethylaminoindole 0.28mol (66.5 g) of 6-N-(p-chloroethoxycarbonyl)aminoindole is added to 200 ml of 4 N sodium hydroxide solution and 66.5 ml of ethanol. The reaction mixture is heated under reflux for 1 hour. The expected product is precipitated by adding ice. It melts at 99 0

C.

Elementary analysis of the product obtained gives the following results: Analysis for CloH 12

N

2 0 C H N O Calculated 68.16 6.86 15.90 9.08 Found 67.88 6.91 15.91 9.15 PREPARATION EXAMPLE 2 Preparation of 6-N-(8-hydroxyethyl)amino-l-methylindole 20 hydrochloride .Step 1 Preparation of N-(6-indolyl)-1,3-oxazolidin-2-one ml of methanol are added to 120 ml of a solution of sodium methylate in methanol and 0.25 mol 25 (60 g) of 6-(p-chloroethoxycarbonyl)aminoindole (prepared in accordance with the first step of Example 1) are then S*6 added,- with stirring. The temperature reaches 50 0

C.

St..rring is continued for 15 minutes after the end of the addition. The precipitate formed is drained, washed with 30 alcohol and then dried. It melts at 199°C.

Analysis of the product recrystallized from acetic acid gives the following results: •Analysis for C 1

H

10

N

2 0 2 C H N O Calculated 65.34 4.98 13.85 15.82 Found 65.42 5.02 13.75 15.86 17 Step 2 Preparation of N-[6-(l-methvl)indolyll-1,3-oxazolidin-2one 100 ml of a 30% solution of sodium methylate in methanol are added to a solution of 0.15 mol (30.5 g) of N-(6-incolyl)-1,3-oxazolidin-2-one in 300 ml of dimethylformamide. The reaction mixture is heated to 40"C. 28 ml of methyl iodide are added dropwise. Heating is continued for 1 hour after the end of the addition. After dilution of the reaction mixture with ice-water, the expected product precipitates. After draining and washing with water and then with ethanol, it melts at 160°C.

Analysis of the product recrystallized from acetic acid gives the following results: *15 Analysis for C 12

H

12

N

2 0, C H N Calculated 66.65 5.59 12.95 14.80 Found 66.55 5.62 12.76 15.08 *S6 Step 3 Preparation of 6-(B-hydroxyethyl)amino-l-methylindole hydrochloride 0.02 mol (4.32 g) of N-[6-(1-methyl)indolyl]-l,3oxazolidin-2-one in 17 ml of 4 N sodium hydroxide solution to which 2 ml of ethanol have been added is heated under reflux for 1 hour. The reaction mixture is diluted with ice-water and the product obtained is then extracted with ethyl acetate.

The oil obtained after evaporation of the ethyl

S

acetate is added to 7 ml of a 7M hydrochloric acid :30 solution in ethanol. The expected product precipitates.

Analysis of the product obtained after washing and drying gives the following results: Analysis for C 11

H

1 5 C1N 2 0 C H Cl N O Calculated 58.28 6.67 15.64 12.36 7.06 Found 58.16 6.70 15.52 12.45 7.13 1 I 18 PREPARATION EXAMPLE 3 Preparation of 6-amino-2,3,4-trimethylindole hydrochloride Step 1 Preparation of 9 g of acetic anhydride are added dropwise to a solution of 12.2 g of 3-methyl-5-nitroaniline in 36 ml of ethyl acetate under reflux. After refluxing for 30 minutes, the mixture is cooled, the precipitate is drained and washed with ethyl acetate (10 ml) and the product is dried. 15.2 g of expected product are obtained.

Analysis of the product recrystallized from ethanol gives the following results: m.p. 185°C.

S *15 Analysis for CHO 1

N

2 0 3 H N Calculated 55.67 5.19 14.43 24.72 Found 55.66 5.20 14.40 24.83 a* Step_ 2 Preparation of ml of ethanol, 25 ml of cyclohexene and then 12.6 g of 3-methyl-5-nitroacetanilide are added to 2.6 g of 10% Pd/C wetted with 2.6 g of water. After refluxing for 2 hours, the suspension is filtered hot and the solid is washed with ethanol (50 ml). The filtrate is evaporated to. dryness under vacuum. 10 g of white precipitate are obtained.

Analysis of the product recrystallized from ethyl acetate gives the following results: 30 m.p. 123°C Analysis for C 9

H

1 Nz 2 0 C H N 0 Calculated 65.83 7.37 17.06 9.74 Found 65.40 7.35 16.94 10.69 Step 3 Preparation of 6-acetamido-2,3,4-trimethylindole 9 g of 3-acetamido-5-methylaniline are dissolved in 20 ml of dimethylformamide and 3.2 ml of 3-bromobutan- 2-one are then added. 'The mixture is left at ambient 19 temperature for 1 hour and the temperature is then raised to 100-110°C for one hour. The mixture is cooled and poured into 100 ml of ice-water. The precipitate is drained and washed successively with 50 ml of distilled water, 20 ml of ethanol and 20 ml of isopropyl ether.

4.2 g of white precipitate are obtained.

Analysis of the product recrystallized from acetic acid gives the following results: m.p. 255"C Analysis for C, 1 Hi 1

N

2 0 C H N 0 Calculated 72.19 7.46 12.95 7.40 Found 71.04 7.52 12.73 8.42 Step 4 Preparation of 6-amino-2,3,4-trimethylindole A suspension of 3.67 g of. 6-acetamido-2,3,4trimethylindole in 15 ml of hydrochloric acid (12 N) is brought to 100 0 C for 3 hours. The mixture is cooled and ,.SS the precipitate is drained and washed successively with .20 3 ml of hydrochloric acid (12 N) and 20 ml of absolute ethanol. 3.5 g of a white precipitate are obtained.

Analysis of the product, gives the following results: Analysis for C 1 His Cl N 2 25 C H Cl N Calculated 62.70 7.18 16.83 13.29 Found 62.72 7.24 17.09 13.22 PREPARATION EXAMPLE 4 Preparation of 6-amino-2,3,7-trimethylindole hydrochloride Step 1 Preparation of 2-methyl-3-nitroacetanilide The procedure is carried out in a manner identical to that in step 1 of Example 3, using 2-methyl-3nitroaniline as the starting material.

Analysis of the product recrystallized from ethanol gives the following results: m.p. 146 0 C repeatedly then 162°C Analysis for CI,,oNzO

I

20 Calculated Found Step 2 Preparation 55.67 55.72

H

5.19 5.27

N

14.43 14.42 0 24.72 24.97 of 2-mrthv1-3-aoatamidoani1 in of 2-met hvl-3-ace tam idoan ili ne~ The procedure is carried out in a manner identical to that in step 2 of Example 3.

Analysis of the product recrystallized from a mixture of ethyl acetate/ethanol gives the following results: m.p. 145°C Analysis for CH 1 iN 2 0 H N 0 was: o000 0e 0 *4 2 0 0 00 2 2 0000 Calculated 65.83 7.37 17.06 9.74 Found 65.76 7.44 17.18 9.71 Step 3 Preparation of 6-acetamido-2,3,7-trimethylindole The procedure cal to that in step 3 Analysis of acetic acid gives the m.p. 242°C Analysis for C,,HiN 2 0 is carried out in a manner identiof Example 3.

the product recrystallized from following results: 0000 goes *00 S 030 *0 0 @0 0 H N 0 Calculated 72.19 7.46 12.95 7.40 Found 72.16 7.46 12.88 7.25 Step 4- Preparation of 6-amino-2,3,7-trimethylindole hydrochloride The procedure is carried out in a manner identical to that in step 4 of Example 3.

Analysis of the product gives the following results: Analysis for C 1

H

15 Cl N 2 Calculated Found 62.70 62.72

H

7.18 7.18 Cl 16.83 17.02

N

13.29 13.31 21 PREPARIA''ION EXAMPLE Preparation of 6-amino-2,3,4,5-tetramethylindole hydrochloride Step 1 Preparation of 2,3-dimethyl-5-nitroacetanilide The procedure is carried out in a manner identical to that in step I of Example 3, using 2,3-dimethylas the starting mateiral.

Analysis of the product recrystallized from ethanol gives the following results: m.p. 230°C Analysis for CloH 12

N

2 0 3 H N 0 15 e g 2 4* e 0 2

S

30 4 o Calculated 57.69 5.81 13.45 23.05 Found 57.77 5.90 13.40 23.12 Step 2 Preparation of 3-acetamido-4,5-dimethylaniline The procedure is carried out in a manner identical to that in step 2 of Example 3.

Analysis of the product recrystallized from ethanol gives the following results: r 162°C Analysis for CloH 14

NO

2 Calculated 67.39

H

7.92

N

15.72 0 8.98 Found 67.38 7.98 15.63 9.08 Step 3 Preparation of 6-acetamido-2,3,4,5-tetramethylindole The procedure is carried out in a manner identical to that in step 3 of Example 3.

Analysis of the product recrystallized from acetic acid gives the following results: m.p. 265°C Analysis for C 14 HzgNzO Calculated Found 73.01 72.93

H

7.88 7.87

N

12.16 12.19

O

6.95 7.07 -22 Step 4 Preparation of 6-amino-2,3,4,5-tetramethylindole hydrochloride The procedure is carried out in a manner identical to that in step 4 of Example 3.

Analysis of the product gives the following results: Analysis for C 12

HICIN

2 C H Cl N Calculated 64.13 7.62 15.78 12.47 Found 64.03 7.71 15.83 12.50 PREPARATION EXAMPLE 6 Preparation of 6-amino-2,3, -dimethyl-5-ethvlindole hydrochloride Step 1 Preparation of ca tThe procedure is carried out in a manner identical to that in step 1 of Example 3, using nitroaniline as the starting material.

Analysis of the product recrystallized from ethanol gives the following results: m.p. 158°C Analysis for C 1 oHIjN 2 0 3 C H N 0 Calculated 57.69 5.81 13.45 23.05 Found_ 57.63 5.82 13.43 22.98 Step 2 Preparation of 3-acetamido-4-ethvlaniline The procedure is carried out in a manner identi- 30 cal to that in step 2 of Example 3.

Analysis of the product recrystallized from ethanol gives the following results: m.p. 150°C Analysis for C 1 oH 14

N.O

C H N 0 Calculated 67.39 7.92 15.72 8.98 Found 67.44 7.93 15.89 9.06 23 Step 3 Preparation of 6-acetamido-2,3-dimethy-5-ethylindole The procedure is carried out in a manner identical to that in step 3 of Example 3.

Analysis of the product recrystallized from acetic acid gives the following results: m.p. 251°C Analysis for C 14

HN

2 0O C H N O Calculated 73.01 7.88 12.16 6.95 Found 72.02 7.88 12.07 6.97 Step 4 Preparation of 6-amino-2,3-dimethyl-5-ethylindole hydrochloride 15 The procedure is carried out in a manner identical ;o that in step 4 of Example 3. S Analysis of the product gives the following results: Analysis for C 12

H,

1 C1N 2 20 C H Cl N Calculated 64.13 7.62 15.78 12.47 Found 73.97 7.70 15.58 12.55 PREPARATION EXAMPLE 7 Preparation of 6-amino-5-chloro-2,3-dimethylindole hydrochloride Step 1 .99. Preparation of The procedure is carried out in a manner identi- Scal to that in step 1 of Example 3, using 30 nitroaniline as the starting material.

:Analysis of the product recrystallized from ethanol gives the following results: m.p. 157°C Analysis for C 8

H

7 Cl N 2 0 3 C H Cl N 0 Calculated 44.77 3.29 16.52 13.05 22.37 Found 44.87 3.30 16.44 13.10 22.24 24 Step 2 Preparation of 3 -acetamido-4-chloroaniline A suspension of 345 g of iron in a mixture of 850 ml of water and 20 ml of acetic acid is brought to 90°C and 172.5 g of 2-chloro-5-nitroacetanilide are added in the course of 45 minutes. After 10 minutes at 95 0

C,

the mixture is cooled and the ferric sludge is filtered off and washed three times with 1 litre of acetone. The filtrate is evaporated to dryness to give 112 g of white precipitate.

Analysis of the product recrystallized from acetone gives the following results: m.p. 198°C Analysis for C 8

H

9 C1 N 2 0 15 C H Cl N 0 Calculated 52.05 4.91 19.2 15.17 8.67 Found 52.10 4.94 19.45 15.24 8.78 Step 3 Preparation of 6-acetamido-5-chloro-2,3-dimethylindole 20 The procedure is carried out in a manner identical to that in step 3 of Example 3.

Analysis of the product recrystallized from acetic acid gives the following results: m.p. 264°C 25 Analysis for C 12

H,

1 C1 NgO C H Cl N 0 Calculated 60.89 5.54 14.98 11.83 6.76 Oe Found 60.78 5.53 15.15 11.86 6.77 Step 4 e**s 30 Preparation of 6-amino-5-chloro-2,3-dimethylindole e hydrochloride The procedure is carried out in a manner identical to that in step 4 of Example 3.

Analysis of the product gives the following results: Analysis for CjOH 12 C1 NzO C H Cl N Calculated 51.97 5.23 30.68 12.12 Found 52.00 5.29 30.63 11.88 25 PREPARATION EXAMPLE 8 Preparation of 6-N-(I--y-dihydroxypropvl)aminoindole 26.4 g of 6-aminoindole are dissolved in 70 ml of absolute alcohol. 29.6 g of glycidol are added and the mixture is stirred for 4 hours at 30-40 0

C.

The mixture is poured into 200 g of ice-water and extracted with 3 times 100 ml of ethyl acetate. The solvent is washed with water. It is dried over Na 2

SO

4 and driven off to dryness under vacuum.

The oily residue is taken up three times in 0.6 litre of isopropyl ether under reflux. The mixture is filtered and the ether is driven off to dryness under vacuum; the residual oil is taken up in 10cc of ethyl acetate and the product is purified on a silica column 15 (eluent ethyl acetate 9/heptane The fraction containing the expected product is evaporated to dryness under vacuum. A colourless oil is obtained which gives the following results: Analysis for C 11

H

14

N

2 0 2 20 Calculated C 64.06 H 6.84 N 13.58 0 15.51 Found C 63.95 H 6.98 N 13.48 0 15.59 EXAMPLES 1 TO 4 The following compositions are prepared: Indole dye xg Ce..

1e e eq..

e a I. C Ce

S

C..

en..

C

*c C 0

I

C

S. C

C

25 potassium iodide yg ethyl alcohol 10.0 g guar gum, sold under the name JAGUAR BP60 by MEYHALL 1.0 g glycoside alkyl ether sold in 60% AS concentration under the name TRITON CG110 by ROHM HAAS 5.0 g AS preservative 0.6 g demineralized water qs 100.0 g The pH is adjusted to the value indicated in the table by adding alkalinizing or acidifying agent, termed "pH agent".

26 EXAMPLE COMPOUND x y pH AGENT pH 1 6-aminoindole 1.0 0.9 citric acid 2 7-aminoindole 1.0 0.9 triethanolamine 3 4-aminoindole 0.6 0.4 citric acid 4 5-aminoindole 0.5 0.45 citric acid Compositions 1 to 4 are applied for 15 minutes to grey hair which is 90% white. After intermediate rinsing, an oxidizing milk at pH 3 assaying at 12.5 volume hydrogen peroxide is applied for 5 minutes. The hair is rinsed again and final shampooing is carried out. The hair is dried.

The hues obtained are as follows: SCOMPOSITION COLOURS 1 chestnut 2 very light, slightly ashy blonde 15 2 very light, slightly ashy blonde 3 very light, slightly ashy blonde 4 light pearly blonde EXAMPLES 5 AND 6 The following compositions are prepared: 20 indole dye 1.0 g potassium iodide 0.5 g ethylene glycol monobutyl ether zl g nonylphenol containing 9 moles of ethylene oxide, sold under the name 25 SINNOPAL NP9 by HENKEL z2 g demineralized water qs 100.0 g 27 EXAMPLE COMPOUND 11 Z2 pH AGENT pH 2,3-dimethyl- 10.0 2.5 triethanolamine 5-amino-6methoxyindole hydrochloride 6 2,3-dimethyl- 17.5 5.0 lactic acid 5-methoxy-6aminoindole Compositions 5 and 6 are applied under the same conditions as compositions 1 to 4.

The hues obtained are as follows: 0 9000 0g** S

S

15 COMPOSITION COLOURS natural golden blonde with a curly tendency light pearly blonde

S

4*SO

S

EXAMPLE 7 6-aminoindole ethyl alcohol potassium iodide guar gum derivative sold under the name JAGUAR HP 60 by MEYHALL glycoside alkyl ether sold under the name TRITON CG 110 by ROHM HAAS preservatives qs spontaneous pH '.1 demineralized water qs 10.0 1.0 g 5.0 g AS 100.0 g This composition is applied for 15 minutes to grey hair which is 90% white. After rinsing, an oxidizing milk at pH 3 assaying at 12.5 volume hydrogen peroxide is applied for 5 minutes. The hair is rinsed, shampooing is carried out and the hair is dried. A deep chestnut 28 colouring is finally obtained.

EXAMPLE 8 COMPOSITION (A) 6-aminoindole 0.5 g ethylene glycol monobutyl ether 12.0 g nonylphenol containing 9 moles of ethylene oxide, sold under the name SINNOPAL NP 9 by HENKEL 20.0 g citric acid qs pH 5.2 demineralized water qs 100.0 g COMPOSITION (B) sodium metaperiodate 3.5 g ethyl alcohol 5.0 g citric acid qs pH demineralized water qs 100.0 g Composition is applied for 20 minutes to grey hair which is 90% white. The hair is rinsed and composi- *tion is then applied for 15 minutes. The hair is rinsed again. After drying, a deep ashy blonde colouring is finally obtained.

EXAMPLE 9 COMPOSITION (A) 6-aminoindole 1.5 g ethyl alcohol 6.5 g propylene glycol 2.0 g nonylphenol containing 9 moles of ethylene oxide sold under the name SINNOPAL NP 9 by HENKEL 14.0 g citric acid qs pH demineralized water qs 100.0 g COMPOSITION (B) sodium nitrite 2.0 g hydrochloric acid qs pH 3.8 demineralized water qs 100.0 g Composition is applied for 20 minutes to grey hair which is 90% white. The hair is rinsed and composition is then applied for 5 minutes. The hair is rinsed and dried. The hair is then dyed in a deep coppery golden blonde hue.

29 EXAMPLE COMPOSITION (A) potassium permanganate 0.40 g hydrochloric acid qs pH demineralized water qs 100.0 g COMPOSITION (B) 6-aminoindole 2.0 g ethylene glycol monoethyl ether 12.0 g polyethylene glycol of MW 280 15.0 g citric acid qs pH demineralized water qs 100.0 g Composition is applied for 15 minutes to grey hair which is 90% white. The hair is rinsed and composition is then applied for 20 minutes. The hair is rinsed again and dried. The final colouring obtained is a natural light chestnut.

EXAMPLE 11

S

S C

C.

S

C..

C

*SCS

S

C

S

COMPOSITION (A) copper sulphate containing 5 moles 20 of water sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER 25 hydroxyethyl cellulose sold under the name CELLOSIZE WP 3H by UNION CARBIDE preservatives qs monoethanolamine qs pH demineralized water qs COMPOSITION (B) 6-aminoindole ethyl alcohol sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER sodium hydroxide solution qs pH demineralized water qs 1.0 g 5.0 g AS 2.4 g AS LOO.0 g 2.2 10.0 5.0 g AS 100.0 g 30 Composition is applied for 5 minutes to grey hair which is 90% white. The hair is rinsed and composition is applied for 10 minutes. The hair is rinsed again and dried. The hair is then dyed in a matt deep golden blonde hue.

EXAMPLE 12 COMPOSITION (A) cerium(III) chloride containing 7 moles of water 1.0 g guar gum derivative sold under the name JAGUAR BP 60 by MEYHALL 0.42 g preservatives qs citric acid qs pH demineralized water qs 100.0 g COMPOSITION (B) 6-aminoindole 1.5 g ethylene glycol monobutyl ether 10.0 g i: nonylphenol containing 9 moles of 0o0 ethylene oxide, sold under the name SINNOPAL NP9 by HENKEL 15.0 g citric acid qs pH demineralized water qs 100.0 g Composition is applied for 10 minutes to grey hair which is 90% white. The hair is rinsed and composi- 25 tion is then applied for 10 minutes. After rinsing again and drying, the hair is coloured in a very light matt golden blonde hue.

31 EXAMPLE 13 COMPOSITION (A) copper sulphate containing 5 moles of water sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by

LEVER

hydroxyethylcellulose sold under the name CELLOSIZE WP 3H by UNION CARBIDE preservatives qs monoethanolamine qs pH demineralized water qs COMPOSITION (B) 15 5-aminoindole ethyl alcohol 1.0 g 5.0 g AS 2.4 g AS 100,0 g .*r 10.0 0 0 *c .:c2

SW.

er sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER 5.0 g AS sodium hydroxide solution qs pH demineralized water qs 100.0 g Grey hair which is 90% white is treated for minutes with composition The hair is rinsed and composition is then applied for 10 minutes. The hair is rinsed again and dried. The hair is then dyed in a matt golden bl.nde hue.

EXAMPLE 14 to:: 30 V 16 COMPOSITION (A) potassium permanganate hydrochloric acid qs pH 3 demineralized water 0.4 g, qs 100.0 g 32 COMPOSITION (B) 4-aminoindole 0.5 g ethylene glycol monobutyl ether 12.0 g nonylphenol containing 9 moles of ethylene oxide, sold under the name SINNOPAL NP9 by HENKEL 20.0 g citric acid qs pH demineralized water qs 100.0 g Composition is applied for 15 minutes to grey hair which is 90% white. The hair is rinsed and composition is then applied for 20 minutes. The hair is rinsed and dried. The hair is then coloured in a deep ashy blonde hue.

EXAMPLE COMPOSITION (A) 2,3-dimethyl-5-amino-6-hydroxyindole o* dihydrobromide 1.0 g ethylene glycol monobutyl ether 12.0 g nonylphenyl containing 9 moles of 20 ethylene oxide, sold under the name SINNOPAL NP9 by HENKEL 20.0 g triethanolamine qs pH 3.7 demineralized water qs 100.0 g COMPOSITION (B) 25 sodium metaperiodate 3.5 g ethyl alcohol 5.0 g citric acid qs pH 4 S' demineralized water qs 100.0 g Composition is applied for 20 minutes to grey 30 hair which is 90% white. After rinsing, composition (B) is applied for 15 minutes. The hair is rinsed again and i dried. A golden blonde is finally obtained.

EXAMPLE 16 6-N-p-hydroxyethylaminoindole 1.0 g potassium iodide 1.0 g ethyl alcohol 10.0 g guar gum derivative sold under the name JAGUAR HP 60 by MEYHALL 1.0 g 33 glycoside alkyl ether sold under the name TRITON CG 110 by ROHM HAAS 5.0 g AS preservatives qs spontaneous pH 7.2 demineralized water qs 100.0 g This composition is applied for 15 minutes to grey hair which is 90% white. The hair is rinsed and an oxidizing milk at pH 3 assaying at 12.5 volume hydrogen peroxide is then applied for 5 minutes. Finally, the hair is dyed in a deep blonde hue with a very matt ashy glint.

EXAMPLE 17 s e 0 0e *5r COMPOSITION (A) 4-aminoindole 0.6 g ethyl alcohol 10.0 g guar gum derivative sold under the name JAGUAR HP 60 by MEYHALL 1.0 g glycoside alkyl ether sold under the name TRITON CG 110 by ROHM HAAS 5.0 g AS preservatives qs 20 spontaneous pH 6.9 demineralized water qs 100.0 g COMPOSITION (B) sodium metaperiodate 5.0 g hydrochloric acid qs pH 3 demineralized water qs 100.0 g Composition is applied for 15 minutes to grey hair which is 90% white. The hair is rinsed and composition is then applied for 15 minutes. The hair is rinsed again and then dried. Hair coloured in a matt ashy 30 deep blonde hue is obtained.

EXAMPLE 18

S

0 5.05

S

0 0O S COMPOSITION (A) 5-aminoindole ethyl alcohol guar gum derivative sold under the name JAGUAR HP 60 by MEYHALL glycoside alkyl ether sold under the name TRITON CG 110 by ROHM HAAS preservatives qs 0.5 g 10.0 g 1.0 g 5.0 g AS 34

S

*e a 00 0 0 0 066

U.S.

0 0 0000 .00.

spontaneous pH demineralized water qs 100.0 g COMPOSITION (B) sodium metaperiodate 5.0 g hydrochloric acid qs pH 3 demineralized water qs 100.0 g Composition is applied for 15 minutes to grey hair which is 90% white. The hair is then rinsed and composition is then applied for 15 minutes. The hair is rinsed again and then dried. Finally, the hair is dyed in a beige golden blonde hue.

EXAMPLE 19 COMPOSITION (A) 6-N-p-hydroxyethylaminoindole 1.0 g ethylene glycol monoethyl ether 10.0 g sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER 5.0 g AS 20 citric acid qs pH 7 demineralized water qs 100.0 g COMPOSITION (B) sodium metaperiodate 3.5 g ethyl alcohol 5.0 g 25 citric acid qs pH 4 demineralized water qs 100.0 g Composition is applied for 20 minutes to grey hair which is 90% white. After rinsing, composition (B) is applied for 15 minutes. The hair is then rinsed again 30 and dried. The hair is finally coloured in an ashy deep blonde hue.

0 5.5.

G a S 0000 0 C 6 S. S EXAMPLE COMPOSITION (A) 7-aminoindole ethyl alcohol guar gum derivative sold under the name JAGUAR HP 60 by MEYHALL glycoside alkyl ether sold under the name TRITON CG 110 by ROHM HAAS 1.0 g 10.0 g 1.0 g 5.0 g AS 35 preservatives qs spontaneous pH 6°7 demineralized water qs 100.0 g COMPOSITION (B) sodium metaperiodate 5.0 g hydrochloric acid qs pH 3 demineralized water qs 100.0 g Composition is applied for 15 minutes to grey hair which is 90% white. The hair is rinsed and composition is then applied for 15 minutes. After rinsing and drying, hair coloured in a deep blonde hue is obtained.

too* 15 s*

S

20 EXAMPLES 21 TO Hair is dyed by applying 60 g of the colouring composition below. The composition is allowed to act for 10 minutes. The hair is then rinsed with an abundant amount of water and rubbed dry and 75 g of the oxidizing composition below is then applied, this composition being allowed to remain on the hair for 10 minutes for Examples 21 to 23 and for 20 minutes for Examples 24 to 25. After rinsing and shampooing, the colouring indicated at the bottom of the table is obtained.

C

S S 'S S 0*VS

S

.S*

S

SS 59 5

S

.00S o 36 in a 21 22 23 24 Colouringr composition 6 -aminoindole -aminoindole 6-p-hydroxyethylaminoindole 4 -aminoindole 6-amino-2 hydroxyin&1a~e. 2HBr 6 -di~vydrx:,,yindole ethyl alcohol hydroxyethylcel lulose sold under the name NATROSOL 250 HHR by HERCULE S glycoside alkyl ether sold as 60% AS under the name TRITON CG 110 by

SEPPIC

sodium lauryl ethersulphate containing 28%

AS

ethylene glycol monobut,-yl ether triethanolainine qs pH spontaneous pH 6 .0 10 10 too* C. 0 5 5 5 'AS) (AS) (AS) 4.2

(AS)

5.2 100 .5 water qsp, 100 6.5 6.5 6.9 100 100 100 00*00: e S SC S S0 37 Oxidizing composi in q 21 tion: 1/3A 2/3B 22 1/3A 2/3B 23 1/3A 2/3B 24 1/3A 2/3B i 2/3A 1/3B 1/3B A) oxyethylenated nonylphenol containing 4 moles of ethylene oxide oxyethylenated nonylphenol containing 9 moles of ethylene oxide ethylene glycol monobutyl ether propylene glycol aqueous ammonia solution monoethanolamine oleic acid diethanol- 20 amide R perfumes, preservatives, sequestering agent water qs 25 B) 20 volume hydrogen peroxide Hues obtained: 26 26 26 26 26 24 24 24 24 24 13 8 19 3.5 qs 100 13 8 19 3.5 qs 100 13 8 19 3,5 qs 100 3.5 qs 100 golden beige blonde qs 100 deep matt hkrde mlrn~ golden coppery ashy coppery deep golden deep auburn blonde blonde EXAMPLE 26 COMPOSITION (A) 2,3-dimethyl-6-aminoindole hydrochloride potassium iodide 35 hydroxyethylcellulose sold under the name NATROSOL 250 HHR by AQUALON glycoside alkyl ether sold as 60% AS under the name TRITON CG 110 by ROHM

HAAS

sodium lauryl ether-sulphate triethanolamine qs pH demineralized water qs 1.0 g 1.0 g 1.0 g 5.0 0.2 g AS g AS 100.0 g 38 COMPOSITION (B) 12.5 volume hydrogen peroxide solution.

Composition is applied for 15 minutes to grey hair which is 90% white. After rinsing, composition (B) is applied for 15 minutes. The hair is rinsed, washed with shampoo and dried.

The hair is dyed a light golden ashy blonde.

EXAMPLE 27 The procedure is as in Example 26, using 1 g of 2,3,7-trimethyl-6-aminoindole hydrochloride instead of 2,3-dimethyl-6-aminoindole hydrochloride.

The dyeing is carried out on permanent-waved grey hair. This is coloured coppery pearly blonde.

EXAMPLE 28 COMPOSITION (A) 2,3,5-trimethyl-6-aminoindole hydrochloride 0.5 g potassium iodide 0.5 g S hydroxyethylcellulose sold under the name 20 NATROSOL 250 HHR by AQUALON 1.0 g glycoside alkyl ether sold as 60% AS under the name TRITON CC 110 by ROHM HAAS 5.0 g AS triethanolamine qs pH 25 demineralized water qs 100.0 g COMPOSITION (B) 12.5 volume hydrogen peroxide solution.

*0 Composition is applied for 15 minutes to permanent-waved grey hair. After rinsing, composition (B) is applied for 15 minutes. After rinsing and shampooing, the hair is dyed light golden ashy blonde.

EXAMPLE 29 COMPOSITION (A) copper sulphate containing 5 molecules of water 1.0 g sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER 3.0 g AS monoethanolamine qs pH 39 demineralized water qs 100.0 g COMPOSITION (B) 2,3,4,5-tetramethyl-6-aminoindole monohydrochloride 0.25 g sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER 4.2 g AS ethylene glycol monobutyl ether 10.0 g 2-amino-2-methylpropan-l-ol qs pH 8.9 demineralized water qs 100.0 g Composition is applied for 10 minutes to grey hair which is 90% white. After rinsing, this hair is t'reated for 15 minutes with composition After rinsing again and drying, the hair is coloured a matt very 15 light golden blonde hue.

EXAMPLE COMPOSITION (A) sodium metaperiodate 5.0 g hydrochloric acid qs pH 20 demineralized water qs 100.0 g COMPOSITION (B) 2,3,4,5-tetramethyl-6-aminoindole monohydrochloride 0.25 g sodium lauryl ether-sulphate containing 25 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER 4.2 g AS ethylene glycol monobutyl ether 10.0 g 2-amino-2-methylpropan-l-ol qs pH 8.9 was**: demineralized water qs 100.0 g 30 Composition is applied for 10 minutes to grey o hair which is 90% white. The said hair is rinsed and treated for 15 i-nutes with composition The hair is rinsed again and dried. The hair is then coloured in an pearly coppery blonde hue.

EXAMPLE 31 COMPOSITION (A) potassium permanganate 1.2 g hydrochloric acid qs pH demineralized water qs 100.0 g 40 COMPOSITION (B) 2-methyl-6-aminoindole 0.1 g N-methyl-6-hydroxyethylaminoindole monohydrochloride 0.1 g 2,3-dimethyl-5-chloro-6-aminoindole monohydrochloride 0.05 g nonylphenol containing 9 moles of ethylene oxide, sold under the name SINNOPAL NP 9 by HENKEL 3.0 g polyethylene glycol 300 10.0 g tetradecyltrimethylammonium bromide 0.1 g ethylene glycol monoethyl ether 4.0 g triethanolamine qs pH 6.6 demineralized water qs 100.0 g 15 Composition is applied for 10 minutes to grey hair which is 90% white and the hair-is rinsed. Composition is then applied for 15 minutes and the hair is rinsed again. The hair then has a golden coppery light chestnut colouring.

20 EXAMPLE 32 COMPOSITION (A) copper sulphate containing 5 molecules of water 1.0 g sodium lauryl ether-sulphate containing 2 moles of ethylene oxide, sold under Sthe name SACTIPON 8533 by LEVER 3.0 g AS monoethanolamine qs pH demineralized water qs 100.0 g COMPOSITION (B) 30 2,3-dimethyl-5-ethyl-6-aminoindole monohydrochloride 0.2 g S amphoteric surfactant termed cocoamphocarboxyglycinate in the CFTA dictionary, sold under the name MIRANOL C2M by MIRANOL 3.0 g AS propane-1,2-diol 12.0 g sodium hydroxide solution qs pH 7.8 demineralized water qs 100.0 g Grey hair which is 90% white is impregnated for 41 minutes with composition After rinsing, it is impregnated for 15 minutes with composition After final rinsing and drying, hair dyed a golden beige blonde hue is obtained.

EXAMPLE 33 COMPOSITION (A) 2-methyl-5-hydroxy-6-aminoindole dihydrobromide 0.25 g 2,3-dimethyl-5-hydroxy-6-aminoindole dihydrobromide 0.15 g amphoteric surfactant termed cocoamphocarboxyglycinate in the CTFA dictionary, sold under the name MIRANOL C2M by MIRANOL 4.0 g ethylene glycol monobutyl ether 8.0 g ethanol 3.0 g N,N-dimethylaminoethanol qs pH 7.6 demineralized water qs 100.0 g COMPOSITION (B) 20 sodium nitrite 1.0 g hydrochloric acid qs pH demineralized water qs 100.0 g Grey hair which is 90% white is treated for minutes with composition After rinsing, said hair is 25 treated for 10 minutes with composition The hair is rinsed again and dried. The hair is finally coloured a coppery golden deep blonde hue.

EXAMPLE 34 S S S* S

S.

BS* S

SS

0*SS sea a a *5*S

S

o COMPOSITION (A) 30 2-methyl-6-aminoindole sodium lauryl e-her-sulphate containing 2 moles of ethylene oxide, sold under the name SACTIPON 8533 by LEVER nonylphenol containing 9 moles of ethylene oxide, sold under the name SINNOPAL NP 9 by

HENKEL

propylene glycol monomethyl ether demineralized water qs spontaneous pH 0.6 g 2.8 g AS 3.0 g 12.0 g- 100.0 g 42 COMPOSITION (B) sodium metaperiodate 5.0 g hydrochloric acid qs pH 3.6 demineralized water qs 100.0 g Composition is applied for 15 minutes to grey hair which is 90% white. After rinsing, the hair is treated for 10 minutes with composition and then rinsed again. After drying, a coppery golden blonde colouring is obtained on this hair.

EXAMPLE Compositions and are identical to those in Example 34.

The sequence of application of the two compositions is merely reversed, maintaining their respective 15 exposure times.

V* Hair dyed a coppery deep blonde hue is finally obtained.

EXAMPLE 36 2-methyl-6-aminoindole 1.0 g 20 potassium iodide 1.0 g S- ethylene glycol monobutyl ether 10.0 g hydroxyethylcellulose is sold under the name NATROSOL 250 HHR by AQUALON 1.0 g glycoside alkyl ether is sold under the 25 name TRITON CG 110 by ROHM HAAS 5.0 g AS preservatives qs demineralized water qs 100.0 g &see spontaneous pH 7.4 This composition is applied for 15 minutes to 30 grey hair which is 90% white. The hair is rinsed and then S* an oxidizing milk at pH 3 assaying at 12.5 volume hydro- S gen peroxide is applied for 5 minutes. After rinsing again, the hair is shampooed and dried. The hair is finally coloured a deep golden coppery blonde hue.

EXAMPLE 37 In the composition of Example 36, 2-methyl-6aminoindole is replaced by the same amount of 6-N-(P,ydihydroxypropyl)aminoindole. The dyeing conditions are identical.

-43 The hair is coloured a deep blonde hue.

to I too to 0

Claims (31)

1. Method for dyeing keratinous fibres, in particular human keratinous fibres, such as hair, characterized in that a composition containing, in a medium appropriate for dyeing, at least one aminoindole corresponding to the formula: Z 2 R4NH Ri RI in which: R 1 and R 3 independently of one another, represent a hydrogen atom or a C1-C4 alkyl group; R 2 denotes hydrogen or a Cl-C4 alkyl group or COOR', R' being a hydrogen atom or a C1-C4 alkyl group; R 4 represents a hydrogen atom or a C1-C4 alkyl, C1-C4 hydroxyalkyl or C2-04 polyhydroxyalkyl group; Z 1 represents a hydrogen or halogen atom or a C1-C4 alkyl group or OR; R being a hydrogen atom or a C1-C4 alkyl group; and Z 2 represents a hydrogen atom or a C1-C4 alkyl group; and its salts is applied to said fibres, the colour being revealed with the aid of an oxidizing system consisting of: iodide ions and hydrogen peroxide, the composition in this case also containing either iodide ions or hydrogen peroxide and the application of the composition being preceded or followed by the application of a composition which contains, in a medium appropriate for dyeing, either: hydrogen peroxide at a pH of between 2 and 12 when the composition contains iodide ions, or Iodide ions at a pH of between 3 and 11, when the composition contains hydrogen peroxide; (ii) nitrites, the application of the composition being followed by the application of an aqueous composition having an acid pH, the composition or the composition containing at least one nitrite; (iii) oxidizing agents chosen from periodic acid and its water- soluble salts, sodium hypochlorite, potassium ferricyanide, silver oxide, Fenton's reagent, lead (IV) oxide and caesium sulphate, these oxidizing agents being present in the composition or being applied separately, at the same time or subsequently, by means of a composition containing them in a medium appropriate for dyeing; (iv) metal anions chosen from the permanganates or bichromates, these oxidizing agents being applied by means of an aqueous composition having a pH of from 2 to 10, before the application of the composition salts of metals of groups III to VIII of the periodic table, these metal salts being applied in a separate step by means of a composition (B) containing these salts in a medium appropriate for dyeing; or (vi) rare earth salts, these rare earth salts being applied by means of a composition containing them in a medium appropriate for dyeing, the composition being applied before or after the application of the composition

2. Method according to claim 1 wherein, in the case where said oxidizing system consists of iodide ions and hydrogen peroxide, composition (B) S contains hydrogen peroxide at a pH between 2 and 7, when the composition (A) contains iodide ions. o

3. Method according to Claim 1 or 2, characterized in that the aminoindole derivatives of formula are chosen from 4-aminoindole, 46 aminoindole, 6-aminoindole, 7-aminoindole, 5-amino-6-methoxy-2,3- dimethylindole, 6-amino-5-methoxy-2,3-dimethylindole, 5-amino-6-hydroxy-2,3- dimethylindole, 5-h ydroxy-6-ami no -2,3-dim ethyl indo le, 6-N-B- hydroxyethylaminoindole, 6-N- -hydroxyethylami no- 1 -m ethyli ndole, 6- methylami noindole, (5 or 6)-amino-N-methylindole, 2-carboxy-6-ami noindole, 4- amino-2,3-dimethylindole, 6-amino-2,3-dimethylindole, 7-amino-2,3- dimethylindole, 6-amino-3-ethyl-2-methylindole, 6-amino-3-methylindole, 6- amino-2-me'thyiindole, 6-amino-2-ethoxy-carbonylindole and 7-amino-3-ethyl-2- methylindole, 6-N- B,,y-dihydroxypropylaminoindole, 2,3,4,5-tetramethyl-6- aminoindole, 2,3-dimethyl-5-chloro-6-aminoindole, 2,3-dimethyl-5-4 aminol ndo le, 2,3 ,4-tri methyl-6-amino-indole, 2-methyl-5-hydroxy-6-aminn. UL

4-methylamino-indole, 4-amino-i -methylindole, 2,3-dimethyl-6-amino-indole, 2,3,7-trimethyl-6-aminoindole, 2,3,5-trimethyl-6-aminoindole and their salts. Method for dyeing keratinous fibres, in particular human keratinous fibres, characterized in that a tinctorial composition containing, in a. cosmetically acceptable carrier having a pH of less than or equal to 7, at (east one indole derivative corresponding to the formula: R3 9*- in which: R, and R 2 which may be identical or different, denote H or OH 3 R 3 denotes H, NH 2 OH or -00H 3 R 4 denotes H, NH- 2 OH or -0C 2 H 5 R 5 denotes H, NH 2 OH or -NHCH 2 CH 2 OH; and R 6 denotes H or OH; A,-EiAA. at least two of the radicals R 3 R 4 R 5 and R 6 denoting hydrogen, and at least one 47 and one only of the groups R 3 R 4 or R 5 denoting NH 2 or -NHCH2C20OH for Rg; and when R 5 denotes an amino group and R 4 denotes OH, Ri and R 2 denote the methyl group, and the salts of corresponding acids, is initially applied to said fibres and in that after an exposure time followed by rinsing anO drying, an alkaline oxidizing solution is subsequently applied, this application being followed by rinsing and shampooing. Method according to Claim 4, characterized in that the aminoindoles of formula (II) are chosen from 4-aminoindole, F 'oindole, 6- aminoindole, 6-amino-2,3-dimethyl-5-hydroxyindole and 6-3- hydroxyethylaminoindole.

6. Method according to any one of Claims 1 to 3, cl ,2ed in that a composition containing, in a medium appropriate for dyeing, the dye of formula in combination with iodide ions is applied to the fibres, the application of the composition being preceded or followed by the application of a composition which contains hydrogen peroxide, in a medium appropriate for dyeing.

7. Method according to any one of Claims 1 to 3, characterized in that a composition containing, in a medium appropriate for dyeing, the dye of Sformula in combination with hydrogen peroxide at a pH of from 2 to 7 is applied, the application of the composition being preceded or followed by the application of a composition which contains iodide ions, in a medium S" appropriate for dyeing.

8. Method according to Claim 6 or 7, characterized in that the iodide ions are chosen from alkali metal iodides, alkaline earth metal iodides or ammonium iodide.

9. Method according to any one of Claims 6 to 8, characterized in that the iodide ions are present in proportions of between 0.007 and 4% by weight, 48 expressed as I- ions, relative to the total weight of the composition or Method according to Claim 9, characterized in that the iodide ions are present in proportions of between 0.08 and 1.5% by weight relative to the total weight of the composition or

11. Method according to Claims 1 to 3, characterized in that the nitrites are chosen from alkali metal or alkaline earth metal nitrites or ammonium nitrite, organic derivatives of nitrites and nitrite carriers, which are present in proportions of between 0.02 and 1 mole/litre.

12. Method according to any one of Claims 1 to 3, characterized in that the oxidizing agents chosen from periodic acid and its water-soluble salt, sodium hypochlorite, potassium ferricyanide, silver oxide, Fenton's reagent, lead (IV) oxide, caesium sulphate and ammonium persulphate are present in proportions of between 0.004 and 0.07 mole per 100 g of composition.

13. Method according to Claim i2 characterized in that said oxidizing agent is present in proportions between 0.01 and 0.04 mole per 100g of composition.

14. Method according to any one of Claims 1 to characterized in that the metal anion is potassium permanganate or sodium bichromate used in anion molar amounts of more than 10-3 moles/1,000 g. Method according to any one of Claims 1 to 3, characterized in that the salts of metals of group III to VIII of the period table are chosen from manganese, cobalt, iron, copper and silver salts used in proportions of between 0.01 and expressed as metal ion.

16. Method according to Claim 15, characterized in that the application of the compositions and is followed by bringing into contact, after rinsing, 49 with a hydrogen peroxide solution to lighten the colour obtained.

17. Method according to any one of Claims 1 to 3, characterized in that the rare earth salts are chosen from the cerium Ce3+ and Ce 4 lanthanum La3+, europium Eu2+ and Eu3+, gadolinium Gd3+, ytterbium Yb2+ and Yb3+ and dysprosium Dy3+ salts.

18. Method according to any one of Claims 1, 2, 3, 6, 7 and 16, characterized in that 1 to 40 volume, hydrogen peroxide solutions are used.

19. Method according to Claim 18 characterized in that 2 to 10 volume hydrogen peroxide solutions are used.

20. Method according to any one of Claims 1 to 19, characterized in that the composition contains the aminoindole of formula or (II) in proportions of between 0.01 and 5% by weight relative to the total weight of the composition.

21. Method according to Claim 20 characterized in that composition 0: contains the aminoindole of formula or (lI) in proportions of between 0.03 and 2.5% by weight relative to the total weight of the composition.

22. Method according to any one of Claims 1 to 21, characterized in that the compositions and are in the form of lotions, thickened to a greater or lesser extent, creams, foams or gels or aerosols.

23. Method according to any one of Claims 1 to 22, characterized in that the medium appropriate for dyeing is an aqueous mediuim, which is cosmetically acceptable when the compositions are intended for dyeing human hair, it being possible for said aqueous medium to consist of water or a water/solvent(s) mixture.

24. Method according to any one of Claims 1 to 23, characterized in that the medium appropriate for dyeing is an anhydrous solvent medium. Method according to Claim 23 or 24, characterized in that the solvents are chosen from ethyl alcohol, propyl alcohol, isopropyl alcohol, tertiary butyl alcohol, ethylene glycol, ethylene glycol monomethyl, monoethyl and monobutyl ethers, ethylene glycol monoethyl ether-acetate, propylene glycol, propylene glycol and dipropylene glycol monomethyl ethers, arJ methyl lactate.

26. Method according to any one of Claims 1 to 23, characterized in that the pH of composition is between 2 and 7.

27. Method according to claim 26, characterized in that the pH of composition is between 3.5 and 7.

28. Method according to any one of Claims 1 to 27, characterized in that the compositions contain fatty amides, surfactants, thickeners, perfumes, sequestering agents, film-forming agents, treatment agents, dispersing agents, conditioning agents, preservatives, opacifying agents, agents for swelling keratinous fibres and any other agent customarily used in tinctorial "compositicns.

29. Process according to any one of Claims 1 to 28, characterized in that the tinctorial composition also contains other indole dyes. Method according to Claim 29, characterized in that the other indole dyes are chosen from 5,6-dihydroxy-indole, 5,6-dihydroxy-2- carboxyindole, 2-methyl-5,6-dihydroxyindole and its corresponding acid addition salt.

31. Method according to Claim 4 or 5, characterized in that the oxidizing sofution contains an oxidizing agent chosen from hydrogen peroxide, urea peroxide and per salts chosen from alkali metal or ammonium percarbonates or perborates.

32. Method according to any one of claims 4, 5 or 31, characterized in that the alkaline agents used in the oxidizing solution are chosen from ammonia and alkanol-amines.

33. Method according to any one of Claims 4, 5 or 31, characterized in that the proportion of oxidizing agent in the oxidizing compositions which are applied to the hair is between 1 and 10% by weight relative to the total weight of the alkaline oxidizing composition.

34. Use, in keratinous fibres dyeing of a composition as defined in any one of claims 1 to 3, 6 to 22, 26 or 27 in association with a composition (B) as defined in any one of claims 1 to 3, 6 to 22, 26 or 27. Dyeing composition for dyeing keratinous fibres when used in accordance with the method as claimed in any one of claims 1 to 9, characterized in that it contains, in a medium appropriate for dyeing, at least one aminoindole corresponding to the formula defined in Claim 1, 2, 3 or 4, and at .jast iodide ions as defined in any one of Claims 1 to 8.

36. Dyeing composition for dyeing keratinous fibres when used in accordance with the method as claimed in claim 1 or 11, characterized in that it contains, in a medium appropriate for dyeing, at least one aminoindole corresponding to the formula defined in Claim 1, and at least one nitrite as defined in Claim 1 or 11. Compounds of formula: Z 2 R 4 HN in which: R 4 denotes hydrogen, C1-C4 alkyl, C1-C4 hydroxy-alkyl or C2-04 polyhydroxyalkyl; Z, denotes hydrogen, alky, or halogen; and Z 2 denotes hydrogen or C1-C4 alkyl; with the proviso that at least one of the radicals Z 1 or Z 2 differs from hydrogen and that the compound 2,3,5-trimethyl 6-aminoindole is excluded from the compounds of formula

38. Compound according to Claim 37, characterized in that it is chosen from 2,3,7-trimethyl-6-aminoindole, 2,3,4,5-tetramethyl-6-aminoindole., 2,3,- dimethyl-5-ethyl-6-aminoindole, 2,3-dimethyl-5-chloro-6-aminoindole and 2,3,4- trimethyl-6-aminoindole. DATED this 13th day of June, 1994 L'OREAL S S WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA