The invention relates to a composition for dyeing keratin fibres, and in particular human keratin fibres such as the hair, comprising at least one para- phenylenediamine derivative substituted with a hepta- methyleneimine nucleus, as oxidation base It is known practice to dye keratin fibres, and in particular human keratin fibres such as the hair, with dye compositions containing oxidation dye precursors, in particular ortho-or para-phenylene- diamines, ortho-or para-aminophenols, heterocyclic compounds such as diaminopyrazole derivatives, pyrazolo [1, 5-a] pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives, 5,6-dihydroxyindole derivatives and 5,6-dihydroxyindoline derivatives, which are generally known as oxidation bases. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds that, when combined with oxidizing products, can give rise to coloured compounds or dyes by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers, the latter being chosen especially from meta-phenylenediamines, meta-aminophenols, meta-hydroxyphenols and certain

heterocyclic compounds such as, for example, pyrazolo- [1, 5-b]-1, 2,4-triazole derivatives, pyrazolo [3,2-c]- 1,2, 4-triazole derivatives, pyrazolo [1, 5-a] pyrimidine derivatives, pyridine derivatives, pyrazol-5-one derivatives, indoline derivatives and indole derivatives.

The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

The"permanent"coloration obtained with these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must have no toxicological drawbacks, it must allow shades to be obtained in the desired intensity, and it must show good resistance to external agents such as light, bad weather, washing, permanent-waving, perspiration and rubbing.

The dyes must also allow white hairs to be covered and, finally, they must be as unselective as possible, i. e. they must produce the smallest possible colour differences along the same length of keratin fibre, which may in fact be differently sensitized (i. e. damaged) between its end and its root. They must also show good chemical stability in the formulations, and must have a good toxicological profile.

In the field of hair dyeing, para-phenylene- diamine and para-tolylenediamine are oxidation bases that are widely used. They give varied shades with

oxidation couplers.

However, there is a need to discover novel oxidation bases that have a better toxicological profile than para-phenylenediamine and para-tolylene- diamine, while at the same time giving the hair excellent properties in terms of colour intensity, variety of shades, colour uniformity and fastness with respect to external agents.

It has already been proposed to use para- phenylenediamine derivatives substituted with a homopiperidine nucleus for the oxidation dyeing of keratin fibres, for example in patent applications FR 2 805 737 to FR 2 805 741 and in patent application WO 98/01106.

The aim of the present patent application is to develop novel compositions for dyeing keratin fibres, comprising para-phenylenediamine derivatives as oxidation base. In particular, the aim of the present invention is to provide novel dye compositions for obtaining strong, unselective and colourfast dyeing of keratin fibres.

This aim is achieved with the present invention, one subject of which is a composition for dyeing keratin fibres, comprising, in a suitable cosmetic dyeing medium, as oxidation base, at least one para-phenylenediamine derivative, one amine of which is included in a ring of heptamethyleneimine type.

By means of the present invention, strong,

unselective and colourfast dyeing of keratin fibres may in particular be obtained.

Another subject of the invention is a process for dyeing keratin fibres using the composition of the present invention, and also the use of a para-phenyl- enediamine derivative as defined above for dyeing keratin fibres.

A subject of the invention is also novel para-phenylenediamine derivatives substituted with a heptamethyleneimine nucleus.

According to one particular embodiment of the invention, the para-phenylenediamine derivative (s), one amine of which is included in a ring of heptamethyleneimine type, is (are) chosen from the compounds of formula (I), or the addition salts thereof: in which: . R represents: - a halogen atom ; - a saturated or unsaturated, linear or branched C1-C8

hydrocarbon-based chain capable of forming a 3-to 6- membered ring, which may comprise one or more oxygen, nitrogen, silicon or sulfur atoms, or an SO2 group; the said radical R not comprising any peroxide bonds, or any diazo, nitro or nitroso radicals; # n is between 0 and 4, it being understood that when n is greater than 2, then the radicals R may be identical or different; # R1 and R2 represent: - a hydrogen atom ; -an alkyl radical, which may be unsaturated; -a hydroxyalkyl radical; -an alkoxyalkyl radical; -an alkylcarbonyl radical; - a hydroxyalkoxyalkyl radical; -an aminoalkyl radical, the amino possibly being mono- or disubstituted with an alkyl, acetyl or hydroxyalkyl radical ; - a hydroxyaminoalkyl radical ; - a carboxyl radical; -a carboxyalkyl radical; - a carbamoyl radical; - a carbamoylalkyl radical; -an alkoxycarbonyl radical; - a mono-or dialkylaminocarbonyl radical ; # R3 represents: -an alkyl radical, which may be unsaturated ; -a hydroxyalkyl radical;

- an alkoxyalkyl radical; - an alkylcarbonyl radical; - a hydroxyalkoxyalkyl radical; - an aminoalkyl radical, the amino possibly being mono- or disubstituted with an alkyl, acetyl or hydroxyalkyl radical; - a hydroxyaminoalkyl radical; - a carboxyl radical ; - a carboxyalkyl radical; - a carbamoyl radical; - a carbamoylalkyl radical; - an alkoxycarbonyl radical; - a mono-or dialkylaminocarbonyl radical ; - a hydroxyl radical; - an alkoxy radical; - a hydroxyalkoxy radical; - an amino radical ; - a mono-or dialkylamino radical; - a hydroxyalkylamino radical ; - a mesylate radical; - a methylsulfonamide radical ; - an alkylcarbonylamino radical ; - a tosylate radical; . a. benzenesulfonamide radical ; m is between 0 and 10, it being understood that when m is greater than 2, then the radicals R3 may be identical or different.

In the above definitions, the alkyl radicals

are linear or branched and comprise, unless otherwise indicated, from 1 to 10 carbon atoms and preferably from 1 to 6 carbon atoms. An alkoxy radical is an alkyl-O-radical, the alkyl radical being as defined above.

The term"unsaturated alkyl radical"means an alkyl of 2 to 10 carbon atoms comprising one or more double and/or triple bonds.

A substituted alkyl radical is a mono- substituted or polysubstituted alkyl radical. For example, a hydroxyalkyl radical or an aminoalkyl radical is an alkyl radical that may be substituted with one or more hydroxyl or amino groups.

In formula (I), the radical R is chosen, for example, from a chlorine atom; a methyl radical; an ethyl radical ; an isopropyl radical; a vinyl radical; an allyl radical; a methoxymethyl radical; a hydroxy- methyl radical; a 1-carboxymethyl radical; a 1-amino- methyl radical; a 2-carboxyethyl radical ; a 2-hydroxy- ethyl radical ; a 3-hydroxypropyl radical ; a 1,2- dihydroxyethyl radical; a 1-hydroxy-2-aminoethyl radical; a 1-amino-2-hydroxyethyl radical; a 1,2- diaminoethyl radical; a methoxy radical ; an ethoxy radical ; an allyloxy radical; a 2-hydroxyethyloxy radical.

In the context of the invention, any range of values defined by the expression"... between... and ..."means that the values delimiting the range are

included therein.

According to one particular embodiment of the invention, R is chosen from an alkyl radical; a hydroxyalkyl radical; an aminoalkyl radical ; an alkoxy radical; a hydroxyalkoxy radical. By way of example, R may be a methyl radical ; a hydroxymethyl radical ; a 2- hydroxyethyl radical; a 1,2-dihydroxyethyl radical; a methoxy radical; a 2-hydroxyethoxy radical.

According to one preferred embodiment of the invention, n is equal to 0 or 1.

According to one particular embodiment of the invention, R1 and R2 are chosen from a hydrogen atom; an alkyl radical; an alkylcarbonyl radical ; a carboxyl radical ; a carbamoyl radical; a mono-or a dialkylcarbamoyl radical; a hydroxyalkyl radical. By way of example, R1 and R2 may be a hydrogen atom and a methyl radical.

According to one particular embodiment of the invention, m is equal to 0 or R3 is chosen from a hydroxyl radical; an alkoxy radical ; an amino radical; a monoalkylamino radical; a dialkylamino radical; an alkyl radical ; a hydroxyalkyl radical; an aminoalkyl radical; a carboxyl radical ; a carbamoyl radical; a hydroxyalkoxyalkyl radical ; a dialkylaminocarbonyl radical. By way of example, R3 may be a hydroxyl radical; a methoxy radical ; a dimethylamino radical ; a hydroxymethyl radical; a methyl radical ; a carbamoyl radical; an aminomethyl radical; a 2-hydroxyethoxy-

methyl radical ; an N, N-dimethylcarbamoyl radical; a 3-hydroxypropyl radical.

The compounds of formula (I) may optionally be salified with strong mineral acids, for instance HC1, HBr or H2SO4, or organic acids, for instance acetic acid, lactic acid, tartaric acid, citric acid or succinic acid.

Examples of derivatives of formula (I) that may be mentioned include the compounds presented in the table below. Formula Nomenclature Formula Nomenclature 4-azocan-1-yl-) 4-azocan-1-yl-2- 0 phenylamine methylphenylamine ! nu, NH NHz tH2 1- (4-aminophen- 1'j 1- (4-amino-3- IJHx N, J NMz N yl) azocane-3- methylphenyl)- I carboxamide azocane-3-carb- NNi NU, oxamide aNHz 4-(3-amlnometh-9 NH2 4-(3-aminometh- NJ z N/z ylazocan-1-yl)-ylazocan-1-yl)-2- i phenylamine methylphenylamine NU2 ()-\ 4-(3-hydroxy-OH 4-(3-hydroxy- N N methylazocan-1-methylazocan-1- I yl) phenylamine yl)-2-methyl- NEZ NI phenylamine 2- [l- (4-amino- 2- [l- (4-amino-3- O N (O N phenyl) azocan- \ methylphenyl)- Ho ethanollmethoxy] ethanol NH2 p '' 0 1- (4-aminophen- 1- (4-amino-3- N yl) azocane-3- methylphenyl)- (N, N-dimethyl)- azocane-3- (N, N- W' NH2 carboxamide dimethyl) carbox- amide H 1- (4-aminophen- 1- (4-amino-3- yl) azocan-5-ol methylphenyl)- azocan-5-ol NU Y NH2 HO 1- (4-aminophen- 1- (4-amino-3- 'N N yl) azocan-4-ol methylphenyl)- azocan-4-ol OHOH H OH HO 1- (4-aminophen- H° 1- (4-amino-3- yl) azocane-4, 5-N methylphenyl)- diol azocane-4, 5-diol NH, NHz 4- (3-methoxy- ao \ 4- (3-methoxyazo- NU J azocan-1-yl)-can-3-yl)-2-meth- phenylamine ylphenylamine NH2 . NHZ N [1- (4-amano-a \ nul phenyl) azocan- methylphenyl) azo- 9 3-yl] dimethyl-NH2 can-3-yl] dimeth- ! NH NH2 amine ylamine 4- (3-methylazo- 2-methyl-4-(3- N M A can-1-yl) phen-A methylazocan-1- w ylamine yl) phenylamine An, NH2 3- [l- (4-amino- 3- [l- (4-amino-3- OH N oH phenyl) azocan- methylphenyl) azo- i NH2 3-yl] propan-1-NH2 can-3-yl] propan-1- ol ol ol ol

Among these compounds, the para-phenylene- diamine derivatives of formula (I) that are particularly preferred are 4-azocan-1-ylphenylamine ; 4-azocan-1-yl-2-methylphenylamine ; 1- (4-aminophenyl)- azocane-4,5-diol ; 1-(4-amino-3-methylphenyl) azocane- 4,5-diol ; 1-(4-aminophenyl)azocan-5-ol ; 1- (4-amino-3- methylphenyl) azocan-5-ol; 1- (4-aminophenyl) azocan-4-ol and 1- (4-amino-3-methylphenyl) azocan-4-ol.

The carbon substituted with Rl, R2 or R3 may be of (R) and/or (S) configuration.

The oxidation base (s) of the invention is (are) each generally present in an amount of between 0. 001% and 10%, and preferably between 0.005% and 6%, by weight approximately relative to the total weight of the dye composition.

The dye composition of the invention may contain one or more couplers conventionally used for dyeing keratin fibres. Among these couplers that may especially be mentioned are meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.

Examples that may be mentioned include 2-methyl-5-aminophenol; 5-N-(ß-hydroxyethyl) amino- 2-methylphenol; 6-chloro-2-methyl-5-aminophenol; 3-aminophenol; 1, 3-dihydroxybenzene ; 1,3-dihydroxy- 2-methylbenzene ; 4-chloro-1, 3-dihydroxybenzene; 2, 4-diamino-l- (p-hydroxyethyloxy) benzene ; 2-amino- 4- (P-hydroxyethylamino)-l-methoxybenzene ; 1,3-diamino- benzene; 1, 3-bis- (2, 4-diaminophenoxy) propane; 3-ureido- aniline; 3-ureido-1-dimethylaminobenzene ; sesamoli 1-ß- hydroxyethylamino-3,4-methylenedioxybenzene ; a-naphthol ; 2-methyl-l-naphthol ; 6-hydroxyindole ; . 4-hydroxyindole ; 4-hydroxy-N-methylindole ; 2-amino-3- hydroxypyridine; 6-hydroxybenzomorpholine; 3,5-diamino- 2,6-dimethoxypyridine ; 1-N- (a-hydroxyethyl) amino-3,4- methylenedioxybenzene; 2,6-bis ( (3-hydroxyethyl- amino) toluene and the addition salts thereof with an

acid.

In the composition of the present invention, the coupler (s) is (are) each generally present in an amount of between 0. 001% and 10% by weight approximately relative to the total weight of the dye composition, and preferably between 0. 005% and 6%.

The composition of the present invention may also comprise one or more additional oxidation bases conventionally used in oxidation dyeing, other than those described above. By way of example, these additional oxidation bases are chosen from para- phenylenediamines other than those described above, bis (phenyl) alkylenediamines, para-aminophenols, bis- para-aminophenols, ortho-aminophenols, ortho- phenylenediamines, heterocyclic bases, and the addition salts thereof.

Among the para-phenylenediamines which can be mentioned, for example, are para-phenylenediamine ; para-tolylenediamine; 2-chloro-para-phenylenediamine; 2,3-dimethyl-para-phenylenediamine ; 2,6-dimethyl-para- phenylenediamine; 2, 6-diethyl-para-phenylenediamine ; 2,5-dimethyl-para-phenylenediamine ; N, N-dimethyl-para- phenylenediamine; N, N-diethyl-para-phenylenediamine ; N, N-dipropyl-para-phenylenediamine; 4-amino-N, N- diethyl-3-methylaniline; N, N-bis (ß-hydroxyethyl)-para- phenylenediamine; 4-N, N-bis ( (3-hydroxyethyl) amino- 2-methylaniline; 4-N, N-bis ( (3-hydroxyethyl) amino- 2-chlooaniline ; 2- ( (3-hydroxyethyl)-para-

phenylenediamine; 2-fluoro-para-phenylenediamine; 2-isopropyl-para-phenylenediamine; N-(ß-hydroxypropyl)- para-phenylenediamine; 2-hydroxymethyl-para-phenylene- diamine ; N, N-dimethyl-3-methyl-para-phenylenediamine; N-ethyl-N-(ß-hydroxyethyl)-para-phenylenediamine ; N- (P, y-dihydroxypropyl)-para-phenylenediamine ; N- (4'- aminophenyl) -para-phenylenediamine; N-phenyl-para- phenylenediamine; 2-ß-hydroxyethyloxy-para-phenylene- diamine; 2-p-acetylaminoethyloxy-para-phenylenediamine ; N-(ß-methoxyethyl)-para-phenylenediamine ; 4- aminophenylpyrrolidine; 2-thienyl-para- phenylenediamine; 2-ß-hydroxyethylamino-5-aminotoluene ; 3-hydroxy-1- (4'-aminophenyl) pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine; para-tolylenediamine ; 2- isopropyl-para-phenylenediamine; 2-(ß-hydroxyethyl)- para-phenylenediamine; 2-(ß-hydroxyethyloxy)-para- phenylenediamine; 2,6-dimethyl-para-phenylenediamine ; 2, 6-diethyl-para-phenylenediamine ; 2, 3-dimethyl-para- phenylenediamine; N, N-bis (ß-hydroxyethyl)-para- phenylenediamine; 2-chloro-para-phenylenediamine; 2-(ß-acetylaminoethyloxy)-para-phenylenediamine and the addition salts thereof with an acid are particularly preferred.

Among the bis (phenyl) alkylenediamines which can be mentioned, for example, are N, N'-bis (ß-hydroxy- ethyl)-N,N'-bis(4'-aminophenyl)-1, 3-diaminopropanol;

N, N'-bis (ß-hydroxyethyl)-N, N'-bis (4'-aminophenyl)- ethylenediamine; N, N'-bis (4-aminophenyl) tetra- methylenediamine ; N, N'-bis (P-hydroxyethyl)-N, N'-bis (4- aminophenyl) tetramethylenediamine ; N, N'-bis (4-methyl- aminophenyl) tetramethylenediamine ; N, N'-bis (ethyl) - N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine ; 1, 8- bis (2,5-diaminophenoxy)-3, 6-dioxaoctane, and the addition salts thereof with an acid.

Among the para-aminophenols which can be mentioned, for example, are para-aminophenol ; 4-amino- 3-methylphenol ; 4-amino-3-fluorophenol ; 4-amino- 3-hydroxymethylphenol ; 4-amino-2-methylphenol; 4-amino- 2-hydroxymethylphenol ; 4-amino-2-methoxymethylphenol; 4-amino-2-aminomethylphenol; 4-amino-2- ( (3-hydroxyethyl- aminomethyl) phenol ; 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols that can be mentioned, for example, are 2-aminophenol; 2-amino-5- methylphenol ; 2-amino-6-methylphenol; 5-acetamido-2- aminophenol, and the addition salts thereof with an acid.

Among the heterocyclic bases, mention may be made, for example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives which may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2, 5-diåminopyridine ; 2- (4-methoxyphenyl) amino-3-amino-

pyridine; 2,3-diamino-6-methoxypyridine ; 2-(ß-methoxy- ethyl) amino-3-amino-6-methoxypyridine; 3,4-diamino- pyridine, and the addition salts thereof with an acid.

Other pyridine oxidation bases that are useful in the present invention are the 3-aminopyrazolo [1, 5-a] pyridine oxidation bases or-the addition salts thereof described, for example, in patent application FR 2 801 308. By way of example, mention may be made of pyrazolo [1, 5-a] pyrid-3-ylamine ; 2-acetylaminopyrazolo [1, 5-a] pyrid-3-ylamine ; 2-morpholin-4-ylpyrazolo [1, 5-a] pyrid-3-ylamine ; 3-aminopyrazolo [1, 5-a] pyridine-2-carboxylic acid ; 2-methoxypyrazolo [1, 5-a] pyrid-3-ylamino; (3-amino- pyrazolo [1, 5-a] pyrid-7-yl) methanol; 2- (3-aminopyrazolo- [1, 5-a] pyrid-5-yl) ethanol; 2- (3-aminopyrazolo [1, 5-a]- pyrid-7-yl) ethanol ; (3-aminopyrazolo [1, 5-a] pyrid-2-yl)- methanol; 3,6-diaminopyrazolo [1, 5-a] pyridine; 3,4-diaminopyrazolo [1, 5-a] pyridine; pyrazolo [1, 5-a] - pyridine-3,7-diamine ; 7-morpholin-4-ylpyrazolo [1, 5-a] - pyrid-3-ylamine ; pyrazolo [1, 5-a] pyridine-3, 5-diamine ; 5-morpholin-4-ylpyrazolo [1, 5-a] pyrid-3-ylamine ; 2- [ (3- aminopyrazolo [1, 5-a] pyrid-5-yl) (2-hydroxyethyl) amino]- ethanol; 2- [ (3-aminopyrazolo [1, 5-a] pyrid-7-yl)- (2-hydroxyethyl) amino] ethanol ; 3-aminopyrazolo- [1, 5-a] pyrid-5-ol ; 3-aminopyrazolo [1, 5-a] pyrid-4-ol ; 3-aminopyrazolo [1, 5-a] pyrid-6-ol; 3-aminopyrazolo- [1, 5-a] pyrid-7-ol and also the addition salts thereof with an acid or with a base.

Among the pyrimidine derivatives which may be mentioned are the compounds described, for example, in patents DE 2 359 399, JP 88-169571, JP 05-63124 and EP 0 770 375 or patent application WO 96/15765, such as 2,4, 5,6-tetraaminopyrimidine, 4-hydroxy-2,5, 6- triaminopyrimidine, 2-hydroxy-4,5, 6-triaminopyrimidine, 2,4-dihydroxy-5, 6-diaminopyrimidine; 2,5, 6- triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A- 2 750 048 and among which mention may be made of pyrazolo [1, 5-a] pyrimidine-3,7-diamine ; 2,5- dimethylpyrazolo [1, 5-a] pyrimidine-3,7-diamine ; pyrazolo [1, 5-a] pyrimidine-3, 5-diamine ; 2,7- dimethylpyrazolo [1, 5-a] pyrimidine-3, 5-diamine ; 3- aminopyrazolo [1, 5-a] pyrimidin-7-ol; 3-aminopyrazolo- [1, 5-a] pyrimidin-5-ol; 2- (3-aminopyrazolo [1, 5-a] - pyrimidin-7-ylamino) ethanol, 2- (7-aminopyrazolo [1, 5- a] pyrimidin-3-ylamino) ethanol, 2- [ (3-aminopyrazolo [1, 5- a] pyrimidin-7-yl) (2-hydroxyethyl) amino] ethanol, 2- [ (7- aminopyrazolo [1, 5-a] pyrimidin-3-yl) (2-hydroxyethyl)- amino] ethanol, 5,6-dimethylpyrazolo [1, 5-a] pyrimidine- 3,7-diamine, 2,6-dimethylpyrazolo [1, 5-a] pyrimidine-3,7- diamine, 2,5, N7, N7-tetramethylpyrazolo [1, 5-a] - pyrimidine-3,7-diamine and 3-amino-5-methyl- 7-imidazolylpropylaminopyrazolo [1, 5-a] pyrimidine, and the addition salts thereof with an acid and the tautomeric forms thereof, when a tautomeric equilibrium exists'.

Among the pyrazole derivatives which may be mentioned are the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4, 5-diamino-1-methylpyrazole ; 4,5- diamino-l- (P-hydroxyethyl) pyrazole; 3,4-diamino- pyrazole ; 4, 5-diamino-1- (4'-chlorobenzyl) pyrazole; 4,5- amino-1, 3-dimethylpyrazole; 4, 5-diamino-3-methyl-1- phenylpyrazole ; 4, 5-diamino-1-methyl-3-phenylpyrazole ; 4-amino-1, 3-dimethyl-5-hydrazinopyrazole; 1-benzyl-4, 5- diamino-3-methylpyrazole ; 4,5-diamino-3-tert-butyl- 1-methylpyrazole ; 4, 5-diamino-1-tert-butyl-3-methyl- pyrazole ; 4, 5-diamino-l- (P-hydroxyethyl)-3-methyl- pyrazole ; 4, 5-diamino-1-ethyl-3-methylpyrazole ; 4,5- diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole ; 4, 5-diamino-l-ethyl-3-hydroxymethylpyrazole ; 4, 5-diamino-3-hydroxymethyl-l-methylpyrazole ; 4, 5-diamino-3-hydroxymethyl-1-isopropylpyrazole; 4, 5-diamino-3-methyl-1-isopropylpyrazole; 4-amino- 5- (2'-aminoethyl) amino-1, 3-dimethylpyrazole ; 3,4, 5-triaminopyrazole; 1-methyl-3, 4,5-triamino- pyrazole ; 3, 5-diamino-l-methyl-4-methylaminopyrazole and 3, 5-diamino-4-(ß-hydroxyethyl) amino-1-methyl- . pyrazole and the addition salts thereof with an acid.

The oxidation base (s) present in the composition of the invention is (are) each generally present in an amount of between 0. 001% and 10% by weight'approximately relative to the total weight of

the dye composition, preferably between 0. 005% and 6%.

In general, the addition salts of the oxidation bases and of the couplers that may be used in the context of the invention are chosen especially from the addition salts with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts with a base, such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen especially from nitrobenzene dyes, azo direct dyes and methine direct dyes. These direct dyes may be of nonionic, anionic or cationic nature.

The cosmetic medium that is suitable for dyeing, also known as the dye support, is a cosmetic medium that generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds that would not be sufficiently soluble in water. As organic solvent, mention may be made, for example, of C1-C4 lower alkanols, such as ethanol and isopropanol ; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The solvents are preferably present in

proportions preferably of between 1% and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5% and 30% by weight approximately.

The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic or amphoteric associative polymeric thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, packaging agents such as, for example, silicones, which may or may not be volatile or modified, film-forming agents, ceramides, preserving agents and opacifiers.

The above adjuvants are generally present in an amount for each of them of between 0. 01% and 20% by weight relative to the weight of the composition.

Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, ot are not substantially, adversely affected by

the addition (s) envisaged.

The pH of the dye composition in accordance with the invention is generally between about 3 and 12 and preferably between about 5 and 11. It may be adjusted to the desired value using acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.

Among the acidifying agents that may be mentioned, for example, are inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

Among the basifying agents that may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di-and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (II) below: in which W is a propylene residue that is optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The dye composition according to the

invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair.

The process of the present invention is a process in which the composition according to the present invention as described above is applied to the fibres, and the colour is developed using an oxidizing agent. The colour may be developed at acidic, neutral or alkaline pH and the oxidizing agent may be added to the composition of the invention just at the time of use, or it may be used starting with an oxidizing composition containing it, which is applied simultaneously or sequentially to the composition of the invention.

According to one particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium that is suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount that is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres. After an action time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin fibres are rinsed, washed with shampoo, rinsed again and then dried.

The oxidizing agents conventionally used for

the oxidation dyeing of keratin fibres are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases. Hydrogen peroxide is particularly preferred.

The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibres ranges preferably between 3 and 12 approximately and even more preferably between 5 and 11. It may be adjusted to the desired value by means of. acidifying or basifying agents usually used in the dyeing of keratin fibres and as defined above.

The ready-to-use composition that is finally applied to the keratin fibres may be in various forms, such as in the form of liquids, creams or gels or any other form that is suitable for dyeing keratin fibres, and especially human hair.

Another subject of the invention is a multi- compartment dyeing device or"kit", in which a first compartment contains the dye composition of the present invention defined above and a second compartment

contains an oxidizing composition. This device may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the Applicant.

Using this device, it is possible to dye keratin fibres using a process that includes mixing a dye composition comprising at least one oxidation base of formula (I) with an oxidizing agent and applying the mixture obtained to the keratin fibres for a time that is sufficient to develop the desired coloration.

A subject of the present invention is also the use for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, of a para-phenylenediamine derivative, one amine of which is included in a ring of heptamethyleneimine type as defined above.

The para-phenylenediamine derivatives of formula (I) other than 5-amino-2-azocan-l-ylbenzoic acid, 4-azocan-1-ylphenylamine and 1- (5-amino-2-azocan- 1-ylphenyl) ethanone are novel and constitute another subject of the invention.

Among the novel para-phenylenediamine derivatives, the ones that are particularly preferred are the para-phenylenediamine derivatives of formula (I'):

in which: RI R'represents : - a halogen atom; - a saturated or unsaturated, linear or branched Ci-Cg hydrocarbon-based chain capable of forming a 3-to 6- membered ring, which may comprise one or more nitrogen, silicon or sulfur atoms, or an SO2 group; the said radical R not comprising any peroxide bonds, or any diazo, nitro or nitroso radicals; . n'is between 0 and 4, it being understood that when n'is greater than 2, then the radicals R may be identical or different ; R'1 and R'2 represent: - a hydrogen atom; - an alkyl radical, which may be unsaturated ; - a hydroxyalkyl radical; - an alkoxyalkyl radical; - an alkylcarbonyl radical ; - a hydroxyalkoxyalkyl radical; - an aminoalkyl radical, the amino possibly being mono- or disubstituted with an alkyl, acetyl or hydroxyalkyl

radical; - a hydroxyaminoalkyl radical; - a carboxyl radical; - a carboxyalkyl radical; - a carbamoyl radical ; - a carbamoylalkyl radical; - an alkoxycarbonyl radical; - a mono-or dialkylaminocarbonyl radical; R'3 represents: -an alkyl radical, which may be unsaturated; a hydroxyalkyl radical; - an alkoxyalkyl radical; - an alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkyl radical, the amino possibly being mono- or disubstituted with an alkyl, acetyl or hydroxyalkyl radical ; - a hydroxyaminoalkyl radical; - a carboxyl radical; - a carboxyalkyl radical; - a carbamoyl radical; - a carbamoylalkyl radical; - an alkoxycarbonyl radical; - a mono-or dialkylaminocarbonyl radical; - a hydroxyl radical; - an alkoxy radical ; - a hydroxyalkoxy radical; - an amino radical ;

- a mono-or dialkylamino radical; - a hydroxyalkylamino radical; - a mesylate radical; - a methylsulfonamide radical; - an alkylcarbonylamino radical; - a tosylate radical; - a benzenesulfonamide radical; mol is between 0 and 10, it being understood that when m'is greater than 2, then the radicals R3 may be identical or different.

The para-phenylenediamine derivatives of formula (I) are obtained by reduction of the para- nitroaniline derivatives of formula (II) below: in which the radicals R, R1, R2 and R3 and the integers n and m are as defined above.

The compounds of formula (II) may be obtained, according to scheme A, by reacting a para- fluoronitrobenzene derivative or a para-chloronitro- benzene derivative with a heptamethyleneimine in basic medium according to a well-known process described especially in: Synthesis 1990 (12), 1147-1148 and Synth.'Commun.--1990, 20 (22), 3537-3545.

The compounds of formula (I) are then obtained, according to scheme A, by reduction of the compounds of formula (II) via the standard reduction methods such as hydrogenation by heterogeneous catalysis in the presence of Pd/C, Pd (II) /C, etc. or alternatively such as a reduction reaction with a metal, for example with zinc, iron, tin, etc. (see Advanced Organic Chemistry, 3rd edition, J. March, Wiley Interscience, and Reduction in Organic Chemistry, M. Hudlicky, Ellis Horwood series chemical Science). (R3) m R1 XR2 (Rs) m \ base reduction r ci- I Ft) n t I f (Rn/ R1 NO2 H l l NO2 NFi2 scheme A The derivatives of formula (II) other than 1- (4-nitrophenyl) azocane, 2-azocan-1-yl-5-nitrobenz- aldehyde and 2-azocan-1-yl-5-nitrobenzoic acid are novel and constitute another subject of the invention.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLE Example 1: synthesis of 4-azocan-1-ylphenylamine dihydrochloride

Step 1: preparation of 1- (4-nitrophenyl) azocane (1) 15.6 g of para-fluoronitrobenzene (0. 110 mol), 15 g of heptamethyleneimine (0.132 mol) and 18.3 g of potassium carbonate (0.168 mol) are placed in 130 ml of water and heated at 90°C with stirring for 8 hours. A brown oil forms and then gives a yellow precipitate after cooling to room temperature.

The yellow solid is filtered off, rinsed thoroughly with water containing 15% sodium chloride, and then dried. 23.4 g of product are obtained, i. e. a yield of 90%.

The results obtained by 1H NMR are as follows: 1H NMR (400 MHz, DMSO) : 1. 75 (m, 6H, CH2) ; 1.95 (m, 4H, CH2) ; 3. 82 (m, 4H, CH2) ; 7. 03 (m, 2H) ; 8.10 (m, 2H).

Step 2: preparation of 4-azocan-1-ylphenylamine dihydrochloride (2) 20 g of 1- (4-nitrophenyl) azocane (1)

(0. 085 mol) and 4 g of 5% palladium on charcoal are placed in 400 ml of absolute ethanol in a 2-litre stainless-steel hydrogenation reactor. The hydrogen- ation is performed at room temperature under a hydrogen pressure of 5 bar for 1 hour 30 minutes. After filtering off the catalyst, 20.2 g of expected product are isolated in the form of the dihydrochloride, i. e. a yield of 85%.

The analysis results are as follows: 1H NMR (400 MHz, D20) : 1.76 (m, 6H, CH2) ; 2.02 (m, 4H, CH2) ; 3.78 (m, 4H, CH2) ; 7.58 (m, 2H); 7.65 (m, 2H).

ESI+ mass: m/z = 205 (MH+).

Elemental analysis for C13H2oN2. 2HCl : Theory (%) : C: 56.32 ; H: 8 ; N: 10.1 ; Cl: 25.58.

Found (%) : C: 55.12 ; H: 8.34 ; N: 8. 98 ; Cl: 23.57.

EXAMPLES OF DYEING Examples 1-14: dye compositions using 4-azocan-1-yl- phenylamine dihydrochloride Examples 1 to 7: dyeing in acidic medium The dye compositions below are prepared: Example 1 2 3 4 5 6 7 4-Azocan-1-ylphenylamine 10-3 10-3 10-3 l0-3 10-3 10-3 10-3 dihydrochloride mol mol mol mol mol mol mol Benzene-1,3-diol 10-3 mol 5 Amino-2-methylphenol lo-3 mol lH-Indol-6-ol 10-3 mol 2-Aminopyrid-3-ol 10-3 mol 3, 6-Dimethyl-lH-pyrazolo-10-3 [5, 1-c] [1, 2,4] triazole mol 2- (2, 4-Diaminophenoxy) ethan- 10-3 ol hydrochloride mol 3-Amino-2-chloro-6-methyl-10-3 phenol hydrochloride mol Dye support (1) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g

(1) : pH 7 dye support 96° ethyl alcohol 20.8 g Sodium metabisulfite as an aqueous 35% solution 0.23 g A. M.

Pentasodium salt of diethylenetriamine- pentaacetic acid as an aqueous 40% solution 0.48 g A. M.

C8-Clo alkyl polyglucoside as an aqueous 60% solution 3.6 g A. M.

Benzyl alcohol 2.0 g Polyethylene glycol containing 8 ethylene oxide units 3.0 g

Na2HP04 0. 28 g KH2PO4 0. 46 g At the time of use, each composition is mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight). A final pH of 7 is obtained.

Each mixture obtained is applied to locks of grey hair containing 90% white hairs. After a leave-in time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. Example 1 2 3 4 5 6 7 Shade Strong Strong Strong Strong Strong Strong Stron observed grey blue-violet-violet-red-blue blue- violet grey grey violet viole Examples 8 to 14: dyeing in basic medium The dye compositions below are prepared:

Example 8 9 10 11 12 13 14 4-Azocan-1-ylphenylamine 10-3 10-3 10-3 10-3 10-3 10-3 10-3 dihydrochloride mol mol mol mol mol mol mol Benzene-1,3-diol 10-3 mol 5-Amino-2-methylphenol 10-3 mol 1H-Indol-6-ol 10-3 mol 2-Aminopyrid-3-ol 10-3 mol 3, 6-Dimethyl-1H-pyrazolo- 10-3 [5, 1-c] [1, 2,4] triazole mol 2- (2, 4-Diaminophenoxy) ethan- 10-3 ol hydrochloride mol 3-Amino-2-chloro-6-methyl-10-3 phenol hydrochloride mol Dye support (2) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs 100g 100g 100g 100g 100g 100g 100g

(2) : pH 9.5 dye support 96° ethyl alcohol 20.8 g Sodium metabisulfite as an aqueous 35% solution 0.23 g A. M.

Pentasodium salt of diethylenetriamine- pentaacetic acid as an aqueous 40% solution 0.48 g A. M.

C8-Clo alkyl polyglucoside as an aqueous 60% solution 3.6 g A. M.

Benzyl alcohol 2.0 g Polyethylene glycol containing 8 ethylene oxide units 3.0 g NH4Cl 4.32 g Aqueous ammonia containing 20% NH3 2.94 g At the time of use, each composition is mixed

with an equal weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight). A final pH of 9.5 is obtained.

Each mixture obtained is applied to locks of grey hair containing 90% white hairs. After a leave-in time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. Example 8 9 10 11 12 13 14 Shade Red-Strong Strong Strong Strong Strong Strong observed brown blue-red-violet-red-blue blue violet violet grey violet grey grey