# US 5,704,948 A · Compositions for dyeing keratinous fibers and keratinous fiber dyeing processes with derivatives of 4-hydroxyindole and oxidation bases

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- Number: US 5,704,948 A
- Document ID: US5704948A
- Status: Granted
- Kind: A
- Application number: 08/678,981
- Filed: 1996-07-12
- Granted: 1998-01-06
- Earliest claimed: 1995-07-13
- Assignees: L'oreal
- Inventors: Eric Terranova; Aziz Fadli; Alain Lagrange
- Web page: https://patentgrep.com/patent/US5704948A

## CPC

- C07D 209/08: with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
- A61K 8/492: {having condensed rings, e.g. indol}
- A61Q 5/10: Preparations for permanently dyeing the hair
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS

## Abstract

A composition for the oxidation dyeing of keratinous fibers containing at least one coupler selected from N-substituted 4-hydroxyindole compounds and acid addition salt thereofs and at least one oxidation base, N-substituted 4-hydroxyindole compounds, a process for synthesizing these substituted compounds, their use as couplers for the oxidation dyeing of keratinous fibers in combination with at least one oxidation base, as well as dyeing processes employing them.

## Claims

### Claim 1

A dyeing composition for keratinous fibers, which comprises: at least one coupler selected from N-substituted 4-hydroxyindole compounds of formula (I) and acid addition salts of said compounds of formula (I): ##STR15## in which: R.sub.1 represents a C.sub.1 -C.sub.4 monohydroxyalkyl radical; a C.sub.2 -C.sub.4 polyhydroxyalkyl radical; a C.sub.1 -C.sub.4 alkoxy(C.sub.1 -C.sub.4)alkyl radical; a C.sub.1 -C.sub.4 hydroxyalkoxy(C.sub.1 -C.sub.4)alkyl radical; a C.sub.1 -C.sub.4 aminoalkyl radical; a C.sub.1 -C.sub.4 aminoalkyl radical whose amine is mono- or disubstituted with a substituent independently selected from a C.sub.1 -C.sub.4 alkyl group, an acetyl group, a C.sub.1 -C.sub.4 monohydroxyalkyl group and a C.sub.2 -C.sub.4 polyhydroxyalkyl group; a C.sub.1 -C.sub.4 alkyl(C.sub.1 -C.sub.4)thioalkyl radical; a C.sub.1 -C.sub.4 monohydroxyalkyl(C.sub.1 -C.sub.4)thioalkyl radical; a C.sub.2 -C.sub.4 polyhydroxyalkyl(C.sub.1 -C.sub.4)thioalkyl radical; a C.sub.1 -C.sub.4 carboxyalkyl radical; a C.sub.1 -C.sub.4 alkoxy(C.sub.1 -C.sub.4)-carbonylalkyl radical; a C.sub.1 -C.sub.4 acetylaminoalkyl radical; a C.sub.1 -C.sub.4 cyanoalkyl radical; a C.sub.1 -C.sub.4 trifluoroalkyl radical; a C.sub.1 -C.sub.4 haloalkyl radical; a C.sub.1 -C.sub.4 phosphoalkyl radical; or a C.sub.1 -C.sub.4 sulphoalkyl radical;
R.sub.2 and R.sub.3, which are identical or different, represent a hydrogen or halogen atom; or a C.sub.1 -C.sub.4 alkyl, a carboxyl, a C.sub.1 -C.sub.4 alkoxycarbonyl or a formyl radical;
R.sub.4 represents a hydrogen or halogen atom; a C.sub.1 -C.sub.4 alkyl radical; a C.sub.1 -C.sub.4 alkoxy radical; an acetylamino radical; a C.sub.1 -C.sub.5 monohydroxyalkyl radical; a C.sub.2 -C.sub.4 polyhydroxyalkyl radical; a C.sub.1 -C.sub.4 alkoxy(C.sub.1 -C.sub.4)alkyl radical; a thiophene radical; a furan radical; a phenyl radical; a C.sub.7 -C.sub.10 aralkyl radical; a phenyl or C.sub.7 -C.sub.10 aralkyl radical which is substituted with at least one substituent selected from a halogen atom, a C.sub.1 -C.sub.4 alkyl radical, a trifluoromethyl radical, a C.sub.1 -C.sub.4 alkoxy radical, an amino radical and an amino radical mono- or independently disubstituted with a C.sub.1 -C.sub.4 alkyl radical; a C.sub.1 -C.sub.4 alkyl(C.sub.1 -C.sub.4)aminoalkyl radical; or a C.sub.1 -C.sub.4 dialkyl(C.sub.1 -C.sub.4)aminoalkyl radical;
wherein for R.sub.1 -R.sub.4 the alkyl and alkoxy groups are linear or branched and the halogen atoms are selected from chlorine, bromine, iodine and fluorine; and
at least one oxidation base.

### Claim 2 (depends on 1)

A dyeing composition according to claim 1, wherein said at least one coupler is selected from:
4-hydroxy-1-N-(.beta.-hydroxyethyl)indole,
4-hydroxy-1-N-(.beta.-hydroxypropyl)indole,
1-N-(.beta.,.gamma.-dihydroxypropyl)-4-hydroxyindole,
4-hydroxy-1-N-(.beta.-hydroxyethyl)-5-methylindole,
4-hydroxy-1-N-(.beta.-hydroxypropyl)-5-methylindole,
1-N-(.beta.,.gamma.-dihydroxypropyl)-4-hydroxy-5-methylindole,
4-hydroxy-1-N-(.beta.-hydroxyethyl)-6-methylindole,
4-hydroxy-1-N-(.beta.-hydroxypropyl)-6-methylindole,
1-N-(.beta.,.gamma.-dihydroxypropyl)-4-hydroxy-6-methylindole,
5-benzyl-4-hydroxy-1-N-(.beta.-hydroxyethyl)indole,
5-benzyl-4-hydroxy-1-N-(.beta.-hydroxypropyl)indole,
5-benzyl-1-N-(.beta.,.gamma.-dihydroxypropyl)-4-hydroxyindole,
4-hydroxy-1-N-(.beta.-hydroxyethyl)-5-.beta.-hydroxy- ethylindole,
4-hydroxy-5-.beta.-hydroxyethyl-1-N-(.beta.-hydroxy- propyl)indole,
1-N-(.beta.,.gamma.-dihydroxypropyl)-4-hydroxy-5-.beta.-hydroxyethylindole,
4-hydroxy-1-N-(.beta.-hydroxyethyl)-5-.beta.,.gamma.-dihydroxypropylindole,
4-hydroxy-1-N-(.beta.-hydroxypropyl)-5-.beta.,.gamma.-dihydroxypropylindole
1-N-(.beta.,.gamma.-dihydroxypropyl)-4-hydroxy-5-.beta.,.gamma.-dihydroxypr opylindole,
1-N-(.gamma.-dimethylaminopropyl)-4-hydroxyindole,
1-N-ethylaminoethyl-4-hydroxyindole,
and the acid addition salts of said compounds.

### Claim 3 (depends on 2)

A dyeing composition according to claim 2, wherein said at least one coupler is selected from:
4-hydroxy-1-N-(.beta.-hydroxyethyl)indole,
4-hydroxy-1-N-(.beta.-hydroxypropyl)indole,
1-N-(.beta.,.gamma.-dihydroxypropyl)-4-hydroxyindole,
4-hydroxy-1-N-(.beta.-hydroxyethyl)-5-methylindole,
1-N-(.gamma.-dimethylaminopropyl)-4-hydroxyindole,
and the acid addition salts of said compounds.

### Claim 4 (depends on 1)

A dyeing composition according to claim 1, wherein the acid addition salts of said compounds of formula (I) are selected from hydrochlorides, hydrobromides, sulphates and tartrates.

### Claim 5 (depends on 1)

A dyeing composition according to claim 1, wherein said at least one coupler represents approximately from 0.0005 to 12% by weight of the total weight of the dyeing composition.

### Claim 6 (depends on 5)

A dyeing composition according to claim 5, wherein said at least one coupler represents approximately from 0.005 to 6% by weight of the total weight of the dyeing composition.

### Claim 7 (depends on 1)

A dyeing composition according to claim 1, wherein said at least one oxidation base is selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and the acid addition salts of said compounds.

### Claim 8 (depends on 1)

A dyeing composition according to claim 1, wherein said at least one oxidation base represents approximately from 0.0005 to 12% by weight of the total weight of the dyeing composition.

### Claim 9 (depends on 8)

A dyeing composition according to claim 8, wherein said at least one oxidation base represents approximately from 0.005 to 6% by weight of the total weight of the dyeing composition.

### Claim 10 (depends on 1)

A dyeing composition according to claim 1, which further comprises at least one additional compound selected from coupler compounds which are different from the N-substituted 4-hydroxyindole compounds of formula (I) and the acid addition salts of said compounds of formula (I) and from direct dyes.

### Claim 11 (depends on 1)

A dyeing composition according to claim 1, wherein said dyeing composition further comprises a medium suitable for dyeing.

### Claim 12 (depends on 1)

A dyeing composition according to claim 1, which has a pH ranging from 3 to 12.

### Claim 13 (depends on 1)

A dyeing composition according to claim 1, which is provided in the form of a liquid, a cream, a gel, or in any other form suitable for dyeing keratinous fibers.

### Claim 14 (depends on 1)

A process for the oxidation dyeing of keratinous fibers, comprising the steps of:
applying to said keratinous fibers an effective amount to develop a color of at least one dyeing composition according to claim 1; and
developing a color at acidic, neutral or alkaline pH using an effective amount of an oxidizing agent which is either added to said dyeing composition at the time of application or is present in an oxidizing composition that is applied to said keratinous fibers either separately from the dyeing composition but at the same time that said dyeing composition is applied to the fibers or sequentially with the dyeing composition.

### Claim 15 (depends on 14)

A process according to claim 14, wherein said dyeing composition is mixed at the time of application with said oxidizing composition and said mixture is then applied to said fibers and allowed to remain in contact with said fibers for a time period ranging from 3 to 50 minutes to develop said color.

### Claim 16 (depends on 15)

A process according to claim 15, wherein said mixture is allowed to remain in contact with said fibers for a time period ranging from 5 to 30 minutes to develop said color.

### Claim 17 (depends on 15)

A process according to claim 15, wherein after said time period, said fibers are rinsed, washed with shampoo, rinsed again and dried.

### Claim 18 (depends on 14)

A process according to claim 14, wherein said oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, and persalts.

### Claim 19 (depends on 18)

A process according to claim 18, wherein said persalts are selected from perborates and persulphates.

### Claim 20 (depends on 1)

A multi-compartment device or multi-compartment dyeing kit, comprising at least two compartments, wherein a first compartment contains a dyeing composition as defined in claim 1, and a second compartment contains an oxidizing composition.

### Claim 21 (depends on 11)

A composition according to claim 11, wherein said medium suitable for dyeing comprises water or a mixture of water and at least one organic solvent selected from C.sub.1 -C.sub.4 lower alkanols, glycerol, glycols, glycol ethers, and aromatic alcohols.