FR2831055A1 - Oxidation dye composition, useful for dyeing keratinic fibers, comprises 1-(2-hydroxyethyl)-4-hydroxyindole as a coupler and a heterocyclic developer - Google Patents

Oxidation dye composition, useful for dyeing keratinic fibers, comprises 1-(2-hydroxyethyl)-4-hydroxyindole as a coupler and a heterocyclic developer Download PDF

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FR2831055A1
FR2831055A1 FR0113764A FR0113764A FR2831055A1 FR 2831055 A1 FR2831055 A1 FR 2831055A1 FR 0113764 A FR0113764 A FR 0113764A FR 0113764 A FR0113764 A FR 0113764A FR 2831055 A1 FR2831055 A1 FR 2831055A1
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FR2831055B1 (en
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Marie Pascale Audousset
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LOreal SA
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4953Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil

Abstract

The subject of the invention is a dyeing composition comprising, in a medium which is suitable for dyeing: at least one heterocyclic base chosen from: (i) 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its salts addition; (ii) cyclic amino paraphenylenediamines and their addition salts (iii) pyrazolo [1,5-a] pyrimidines and their addition salts; at least 1-N- (β-hydroxyethyl) 4-hydroxyindole and its addition salts as coupler. The subject of the invention is also the use of this composition for dyeing keratinous fibers as well as the dyeing process using this composition. </ P>

Description

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TINCTORIAL COMPOSITION COMPRISING AT LEAST ONE HETEROCYCLIC BASE AND T-N- (p-HYDROXYETHYL) 4-HYDROXY INDOLE AS A COUPLER; The subject of the invention is a dyeing composition comprising, in a medium which is suitable for dyeing: at least one heterocyclic base chosen from: (i) 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its salts addition; (ii) cyclic amino paraphenylenediamines and their addition salts; (iii) pyrazolo [1,5-a] pyrimidines and their addition salts; - at least ! t-N- (p-hydroxyethyl) 4-hydroxyindole and its addition salts as coupler.

The subject of the invention is also the use of this composition for dyeing keratinous fibers as well as the dyeing process using this composition.

It is known to dye keratinous fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as than indolic compounds.

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The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors.

The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and friction.

The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its point and its root.

Patent application FR 2,736,640 has already proposed compositions for the oxidation dyeing of keratin fibers containing as couplers an N-substituted derivative of 4-hydroxyindol associated with oxidation bases.

Patent applications FR-A-2 750 048 and FR 2 791 563 also disclose compositions for the oxidation dyeing of keratinous fibers containing, as oxidation base, pyrazolo [1,5-a] ] -pyrimidines Associated with Other Oxidation Bases and One or More Couplers An example of a composition comprising, as the oxidation bases, the paraphenylenediamine combination (1% by weight), is particularly known in patent application FR 2 791 563, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine, 2HCl (3% by weight and as couplers: 1-N- (ss-hydroxyethyl) 4-hydroxyindole) (1) 2% by weight) and 3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole (1.2% by weight). The presence of 3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole impairs the stability of the composition and also induces staining of the clothing.

Keratinous fiber dye compositions comprising 4,5-diaminopyrazole derivatives which may be substituted in the 2-position by alkyl or hydroxyalkyl radicals have been proposed in DE 3843892 patent applications.

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 Patent Application EP 692 245 discloses dye compositions comprising 4,5-diaminopyrazole derivatives associated with particular metaphenylenediamines. Patent Application DE 19643059 describes dyeing compositions combining 4,5-diaminopyrazole derivatives with meta-aminophenol and metaphenylenediamine couplers. Patent Application DE 19646609 describes dyeing compositions combining 4,5-diaminopyrazole derivatives with benzoxazine couplers.

It is moreover known in the patent application JP 11158048 to use dye compositions comprising paraphenylenediamine derivatives, one of the nitrogen atoms is included in a 5- to 7-membered ring. US Pat. No. 5,851,237 proposes the use of optionally substituted 1- (4-aminophenyl) pyrrolidine derivatives on the benzene ring to replace para-phenylenediamine. No. 5,993,491 proposes the use of N- (4-aminophenyl) -2- (hydroxymethyl) -pyrrolidine derivatives optionally substituted on the benzene ring to replace para-phenylenediamine.

However, the colorations obtained by using these dyeing compositions are not always powerful enough, aesthetic, chromatic or sufficiently resistant to the various attacks that can suffer the hair.

However, the Applicant has now discovered that it is possible to obtain, without the disadvantages of the dyeing compositions of the prior art, new dyes, capable of leading to colorations with varied shades, chromatic, powerful, aesthetic, not very selective and resistant to the various attacks that the fibers may undergo, by combining at least one heterocyclic oxidation base chosen from (i) 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its addition salts; (ii) cyclic amino paraphenylenediamines and their addition salts;

Figure img00030001

(iii) pyrazolo [1,5-a] pyrimidines and their addition salts; with N- (p-hydroxyethyl) -4-hydroxyindole of formula:

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Figure img00040001

or one of its addition salts as a coupler; said composition not containing 3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole.

The invention also relates to a dyeing process using this composition.

Another subject of the invention is the use of the composition of the present invention for dyeing keratinous fibers, in particular human keratinous fibers such as the hair.

The composition of the present invention makes it possible in particular to obtain a coloring of keratinous chromatic fibers, which is very powerful, not very selective and tenacious while avoiding the degradation of these fibers.

In the context of the present invention, alkyl is understood to mean linear or branched radicals, for example methyl, ethyl, n-propyl, iso-propyl or butyl, etc. An alkoxy radical is an alk-O radical, the alkyl radical having the definition given above.

Halogen is preferably CI, Br, I, F.

Among the para-phenylenediamines containing a cyclic amino group that may be used in the dyeing compositions in accordance with the invention, mention may be made of the para-phenylenediamine derivatives of formula (1) below, or their addition salts:

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Figure img00050001

in which - Z represents the atoms necessary to form a saturated ring of 3 to 8 members, these atoms possibly being carbon or nitrogen atoms, preferably only carbon atoms, the ring being able to be substituted, - R1 represents a hydrogen atom; a halogen atom selected from a chlorine and bromine atom; a linear or branched saturated or unsaturated C 1 -C 7 hydrocarbon-based chain of which one or more carbon atoms can be replaced by an oxygen, nitrogen or sulfur atom or by a SO 2 group, and whose carbon atoms can to be, independently of one another, substituted by one or more halogen atoms; said radical R1 having no peroxide bond, or diazo, nitro or nitroso radicals, According to the present invention, the ring formed with Z and the nitrogen atom of para-phenylenediamine may be a pyrrolidine, piperidine, homopiperidine or imidazoline ring. , pyrazolidine, piperazine. The saturated cycle thus formed can be substituted. By way of example, the halogen atoms, the hydroxyl radical, the amino radical or the C 1 -C 4 alkyl radicals may optionally be substituted by one or more hydroxyl, amino or (di) alkylamino radicals. C2, carboxy; the carboxy radical; carbamoyl or sulfonamido radicals; the radicals-OR4 in which R4 represents a C1-C4 alkyl radical substituted with one or more radicals chosen from a halogen atom, C1-C2 alkoxy, amino, C1-C2 aminoalkyl or C3-C4 alkyl radicals; substituted with one or more hydroxyl radicals; a methylcarbonyl radical; a radical-NR5R6 in which Rs and Re represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical substituted with one or more radicals chosen from a halogen atom, the hydroxyl radicals; , C1-C2 alkoxy, amino or C1-C2 aminoalkyl.

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 According to a particular embodiment, Z represents the carbon atoms necessary to form a 5- to 8-membered ring, preferably a substituted or unsubstituted pyrrolidine ring.

According to the invention, a saturated or unsaturated, linear or branched hydrocarbon chain of the formula (1) is a chain which may comprise one or more double bonds and / or one or more triple bonds, and may form one or more rings comprising 3 to 6 members, the double bonds possibly leading to aromatic groups. When it is stated that one or more of the carbon atoms of R 1 may be replaced by an oxygen, nitrogen or sulfur atom or by a group SO 2, and / or that said radical R 1 may be unsaturated, this means

Figure img00060001

that we can, by way of example, make the following transformations:
Figure img00060002

1 -CH-H can become -OH zu: ~ O can become: ~ O 1 1 can become! '- SOUND 1 2 1 O can become eo) <JO 1 1 1 1 According to the invention, R1 represents preferably a hydrogen atom, an alkyl radical, an alkenyl radical, an alkynyl radical, an alkoxyalkyl radical, a hydroxyalkyl radical, an alkoxy radical, an allyloxy radical, a hydroxyaminoalkyl radical, a hydroxyalkoxy radical, a carboxyalkyl radical or an aminoalkyl radical; .

By way of example, mention may be made for R 1 of the radicals methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-

Figure img00060003

carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or 2-hydroxyethyloxy. Preferably, R2 represents a hydrogen atom, a methyl radical, hydroxymethyl, 2-

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 hydroxyethyl, 1, 2-dihydroxyethyl, methoxy or 2-hydroxyethoxy, preferably a hydrogen atom or a methyl radical.

According to a particular embodiment, the oxidation base chosen from paraphenylenediamine derivatives is a paraphenylediamine derivative with a pyrrolidine group corresponding to the following formula (Ia)

Figure img00070001

in which - R 1 is as defined above, - R2 represents a hydrogen atom; a hydroxyl radical; an amino radical; a radical -OR4 in which R4 represents a C1-C4 alkyl radical substituted with one or more radicals chosen from a halogen atom, C1-C2 alkoxy, amino, C1-C2 aminoalkyl or mono-or poly-alkyl radicals; C1-C4 hydroxyalkyl; a methylcarbonyl radical; a radical -NRsR6 in which R5 and R6 represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical which may be substituted by one or more radicals chosen from a halogen atom, and hydroxyl, C 1 -C 2 alkoxy, amino or C 1 -C 20 aminoalkyl radicals; - R3 represents a hydrogen atom; a carbamoyl radical, an amido radical; a mono-or poly-hydroxy-C 1 -C 5 radical.

According to a particular embodiment, R2 represents a hydrogen atom, a hydroxyl, acetoxy, amino, alkylamino or hydroxyalkylamino radical.

By way of example, mention may be made for R 2 of a hydrogen atom, a hydroxyl, acetoxy, amino, methylamino, dimethylamino or 2-hydroxyethylamino radical. Preferably, R2 represents a hydrogen atom, a hydroxyl radical or an amino radical.

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Figure img00080001

In formula (Ia), R3 preferably represents a hydrogen atom, a carbamoyl radical, a hydroxyl radical, a C1-C4 hydroxyalkyl radical or a methyl radical.

By way of example, the paraphenylenediamine derivatives of formula (1) are chosen from N- (4-aminophenyl) -3-hydroxy-pyrrolidine, N- (4-amino-2-methylphenyl) -3-hydroxypyrrolidine, N - (4-Amino-2-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-methoxypenyl) -3-hydoxy-pyrrolidine, N- (4-amin) -2- (2) hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1, 2-dihydroxyethyl) phenyl) ) -3-hydroxypyrrolidine, N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3- methoxyphenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1-hydroxyethyl) phenyl) -3- hydroxypyrrolidine, N- (4-amino-3- (1,2-dihydroxyethyl) phenyl) -3-hydroxy-pyrrolidine, N- (4-amino-phenyl) -3-aminopyrrolidine, N- (4- amino-2-methyl-phenyl) -3aminopyrrolidine, N- (4-amino-2-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-2-methoxyphenyl) -3-aminopyrrolidine, N- (4-amino-2- (2-hydroxy-ethyl) phenyl) 3-aminopyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-2- (1,2-dihydroxyethyl) phenyl) -3-hydroxy-pyrrolidine, N- (4-amino-3-methylphenyl) -3-aminopyrrolidine, N- (4-amino-3-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-3-methoxyphenyl) -3-am! no-pyrro! N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-3- (1-hydroxyethyl) phenyl) -aminopyrrolidine, N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine; (4-amino-3- (1, 2-dihydroxyethyl) phenyl) -3-aminopyrroline, 1- (4-aminophenyl) -pyrrolidine, 1- (4-aminophenyl) -2-pyrrolidinemethanol, 1- (4-aminophenyl) 4-hydroxy-2-pyrrolidinemethanol, N- (4-aminophenyl) -prolineamide and their addition salts with an acid. Preferably, the paraphenylenediamine derivatives of formula (IIa) are chosen from 3-hydroxy-1- (4'-aminophenyl) pyrrole. idine, 3-amino 1- (4'-aminophenyl) pyrrolidine, 1- (4-aminophenyl) pyrrolidine, 1- (4-aminophenyl) -2-pyrrolidinemethanol, 1- (4-aminophenyl) -4-hydroxy -2-pyrrolidinemethanol, N- (4-aminophenyl) -prolineamide and their addition salts.

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Among the pyrazolo [1, 5-a] -pyrimidines which can be used as oxidation base in the dyeing composition in accordance with the invention, mention may especially be made of the compounds of the following formula (II), and their addition salts with an acid or with a base:

Figure img00090001

in which: R7 Ra, Rg and R10 denote, identical or different, a hydrogen atom; a C1-C4 alkyl radical; an aryl radical; a C1-C4 hydroxyalkyl radical; a C2-C4 polyhydroxyalkyl radical; a (C1-C4) alkoxy C1-C4 alkyl radical; a C1-C4 amino alkyl radical; a C 1 -C 4 alkylamino radical whose amine is protected by an acetyl, ureido or sulfonyl radical; a (C1-C4) alkylamino (C1-C4) alkyl radical; a di- [(CrC4) alkyl] amino C1-C4 alkyl radical in which the dialkyls can form a 5- or 6-membered aliphatic or heterocyclic ring; a hydroxy (C1-C4) alkyl- or di- [hydroxy (C1-C4) alkyl] -amino (C1-C4) alkyl radical - the radicals X denote, identical or different, a hydrogen atom or a C1-alkyl radical; -C4, an aryl radical, a C1-C4 hydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a C1-C4 aminoalkyl radical, a (C1-C4) alkylamino (C1-C4) alkyl radical, a di - [(C1-C4) alkyl] C1-C4 alkyl in which the dialkyls can form a 5- or 6-membered aliphatic or heterocyclic ring, a hydroxy (C1-C4) alkyl- or di- [hydroxy (C1- C4) alkyl] C1-C4 alkyl, amino, (C1-C4) alkyl- or di - [(C1-C4) alkyl] amino; a halogen atom, a carboxylic acid group, or a sulfonic acid group; i is 0, 1, 2 or 3; p is 0 or 1; q is 0 or 1; n is 0 or 1; provided that: - (i) the sum p + q is different from 0; - (ii) when p + q is 2, then n is 0 and the groups NR6R7 and NRsRg occupy the positions (2,3); (5.6); (6.7); (3,5) or (3,7);

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 - (iii) when p + q is equal to 1 then n is 1 and the NR6R7 (or NRgRg) group and the OH group occupy the positions (2,3); (5, 6); (6.7); (3, 5) or (3,7).

The pyrazolo [1, Sa] -pyrimidines of formula (II) used as oxidation base in the dye composition according to the invention are known compounds and described in the patent application FR-A-2 750 048 the content of which forms an integral part of this application.

Among the pyrazolo- [1, Sa] -pyrimidines of formula (II) above, mention may be made in particular of:

Figure img00100001

pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2-methyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,1'-Sa] pyrimidine-3,7-diamine; pyrazolo [1,1'-Sa] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1, Sa] -pyrimidin-7-01; 3-amino-5-methyl pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo- [1, sa] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; 3-amino-7-ss-hydroxyethylamino-5-methyl-pyrazolo [1,5-a] pyrimidine; 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;
Figure img00100002

S, 6-dimethyl pyrazolo [1,1'-Sa] pyrimidine-3,7-diamine; 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5, N-7, N-7-tetramethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine; and their addition salts.

The composition of the present invention may further comprise one or more additional oxidation bases conventionally used in oxidation dyeing other than those described above. By way of example, these oxidation bases

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Figure img00110001

additional are selected from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than those previously described and their addition salts.

Among the paraphenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diisyl-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- (sshydroxyethyl) paraphenylenediamine, 4-N, N-bis- (p-hydroxyethyl) amino-2-methyl aniline, 4-N, N-bis- (p-hydroxyethyl) amino 2-chloroaniline, 2-ss hydroxy-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (ss-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl) p-hydroxyethyl) paraphenylenediamine, N- (p, dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-ss-hydroxyethyloxy para-phenylenediamine, 2-ss-acetylaminoethyloxy para-phenylenediamine, N- (p-methoxyethyl) ) paraphenylenediamine, 2-thienyl paraphenylenediamine, 2-ss hydroxyethylamino 5-amino toluene and their addition salts.

Among the para-phenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-ss-hydroxyethyl paraphenylenediamine, 2-ss-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6 ethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis (ss-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-ss-acetylaminoethyloxy-para-phenylenediamine, and their addition salts are particularly preferred.

Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (phydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) -bis- (sshydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine

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 tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N Bis (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and salts thereof addition.

Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplary; methyl phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ss-hydroxyethylaminomethyl) phenol, 4-amino-2-fluorine phenol, and their addition salts.

Among the ortho-aminophenols, mention may be made, by way of example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino phenol, and their salts. 'addition.

Among the heterocyclic bases, mention may be made, by way of example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives other than those mentioned above.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2, 3-diamino 6-methoxy pyridine, 2- (3-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts.

Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1, 5-a] -pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. By way of example, mention may be made

Figure img00120001

pyrazol 5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo 5-a] pyridin-3-ylamine; 3-aminopyrazol 5-a] pyridin-2-carboxylic acid, 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino

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pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-

Figure img00130001

amino-pyrazol 5-a] pyridine-5-01; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol as well as their addition.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2, 4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine 2,4 -dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and their tautomeric forms, when tautomeric equilibrium exists.

Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-methyl pyrazole, 4,5-diamino 1- (ss-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5 1-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethylhydrazino pyrazole, 1-benzyl 4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5 1-ethyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl-pyrazole, 4,5-diamino-3-hydroxymethyl 1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-amin) oethyl) amino, 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, diamino 4- (5-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts.

<Desc / Clms Page number 14>

 The oxidation base (s) present in the composition of the invention are in general each present in an amount of between 0.001 to 10% by weight approximately of the total weight of the dyeing composition, preferably between 0.005 and 6%.

The composition according to the invention may contain in addition to 4-hydroxy-N-hydroxyethylindole one or more additional couplers conventionally used for dyeing keratinous fibers. Among these couplers, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers other than 4-hydroxy-N-hydroxyethylindole and their addition salts.

By way of example, mention may be made of 2-methyl-5-aminophenol, 5-N- (ss-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol and 3-amino. phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (S-hydroxyethoxy) benzene, 2-amino-4 - (sshydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, -ss-hydroxethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N -methylindole, 2- amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (ss-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis - (5-hydroxyethylamino) toluene and their addition salts.

In the composition of the present invention, the coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

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

<Desc / Clms Page number 15>

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

The medium suitable for dyeing, also known as dyeing medium, generally consists of water or a mixture of water and at least one organic solvent for solubilizing compounds that are not sufficiently soluble in water. As organic solvent, there may be mentioned, for example lower C1-C4 alkanols, such as methanol 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 may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

<Desc / Clms Page number 16>

Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratinous fibers or else using conventional buffer systems.

Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

Among the alkalinizing agents, mention may be made, for example, of ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (III):

Figure img00160001

wherein West a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Re 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, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair.

<Desc / Clms Page number 17>

The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers, and the color is revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied simultaneously or sequentially to the composition of the invention According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried.

The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

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

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

<Desc / Clms Page number 18>

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

The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition defined above and a second compartment contains an oxidizing composition. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant.

From this device, it is possible to dye the keratinous fibers from a process which comprises mixing a dye composition according to the invention with an oxidizing agent as defined above, and the application of the mixture obtained. on the keratinous fibers for a time sufficient to develop the desired coloration.

Figure img00180001

The following examples serve to illustrate the invention without being limiting in nature.

<Desc / Clms Page number 19>

EXAMPLES OF FORMULATION The following dye compositions were prepared (contents in grams):

Figure img00190001

<Tb>
<tb> Compositions1234
<tb> 1,075
<tb> 4, <SEP> 5-diamino-1-2 hydroxyethyl) pyrazole, <SEP> dihydrochloride
<tb> (oxidation base <SEP>)
<tb> pyrazolo [1,5-a] pyrimidine-3,7- <SEP> - <SEP> 0.311
<tb> diamine, <SEP> dihydrochloride
<tb> (oxidation base <SEP>)
<tb> 3-Amino-7-methylamino-pyrazolo- <SEP> 1, <SEP> 180
<tb> [1,5-a] -pyrimidine-3, <SEP> 7-diamine,
<tb> dihydrochloride <SEP> (base <SEP> oxidation)
<tb> N-4-aminophenyl <SEP> 3-hydroxy- <SEP> - <SEP> - <SEP> - <SEP> 1.255
<tb> pyrrolidine <SEP> (oxidation base <SEP>)
<tb> 4-hydroxy <SEP> 1-N- (ss-hydroxyethyl) <SEP> indole <SEP> 0.885 <SEP> 0.248 <SEP> 0.885 <SEP> 0.885
<tb> (coupler)
<tb> Support <SEP> of <SEP> common <SEP> dyeing
<tb> Demineralized <SEP> Water <SEP> q. <SEP> s. <SEP> p. <SEP> 100g <SEP> 100g <SEP> 100g <SEP> 100g
<Tb>

Figure img00190002

<Tb>
<tb> (**) <SEP>: <SEP> support <SEP> of <SEP> dye <SEP> common <SEP>:
<tb> - <SEP> Alcohol <SEP> Oleic <SEP> polyglycerolated <SEP> to <SEP> 2 <SEP> moles <SEP> of <SEP> glycerol <SEP> 4, <SEP> 0g
<tb> - <SEP> Alcohol <SEP> Oleic <SEP> polyglycerolated <SEP> at <SEP> 4 <SEP> moles <SEP> of <SEP> glycerol <SEP> at <SEP> 78 <SEP>% <SEP > from
<tb> active <SEP> materials <SEP> (M. <SEP> A. <SEP>) <SEP> 5,69g <SEP> M. <SEP> A.
<Tb>

- <SEP> Oleic <SEP> acid <SEP> 3, <SEP> 0g
<tb> - <SEP> Amine <SEP> oleic <SEP> to <SEP> 2 <SEP> moles <SEP> of oxide <SEP> of ethylene <SEP> sold <SEP> under <SEP>
<tb> denomination <SEP> commercial <SEP> ETHOMEEN <SEP> 012 <SEP> by <SEP> the <SEP> company <SEP> AKZO <SEP> 7, <SEP> 0g
<tb> - <SEP> Laurylamino <SEP> succinamate <SEP> of <SEP> diethylaminopropyl, <SEP> salt <SEP> of <SEP> sodium
<Tb>

<Desc / Clms Page number 20>

Figure img00200001

<Tb>
<tb> to <SEP> 55 <SEP>% <SEP> from <SEP> M. <SEP> A. <SEP> 3, <SEP> 0g <SEP> M. <SEP> A.
<Tb>

Alcohol <SEP> Oleic <SEP> 5, <SEP> Og
<tb> diethanolamide <SEP> of <SEP> oleic acid <SEP> 12, <SEP> 0g
<tb> - <SEP> Propylene Glycol <SEP> 3.5g
<tb> - <SEP> Alcohol <SEP> ethyl <SEP> 7, <SEP> 0g
<tb> - <SEP> Dipropylene Glycol <SEP> 0.5g
<tb> - <SEP> Monomethyl Ether <SEP> of <SEP> Propylene Glycol <SEP> 9, <SEP> 0g
<tb> - <SEP> Metabisuifite <SEP> from <SEP> sodium <SEP> to <SEP> in <SEP> solution <SEP> aqueous <SEP> to <SEP> 35 <SEP>% <SEP> from <SEP > M. <SEP> A. <SEP> 0.455g <SEP> M. <SEP> A.
<Tb>

- <SEP> Acetate <SEP> Ammonium <SEP> 0.8g
<tb> - <SEP> Antioxidant, <SEP> sequestering <SEP> q. <SEP> s.
<Tb>

- <SEP> Fragrance, <SEP> preservative <SEP> q. <SEP> s.
<Tb>

- <SEP> Ammonia <SEP> to <SEP> 20 <SEP>% <SEP> of <SEP> NH3 <SEP> 10, <SEP> 0g
<Tb>
At the time of use, each dye composition 1 to 4 was mixed with an equal weight of hydrogen peroxide at 20 volumes of pH 3 (6% by weight).

Each mixture obtained was applied for 30 minutes, on strands of gray hair natural to 90% of white permed at a rate of 30g for 3g of hair. After rinsing, washing with standard shampoo and drying, the locks were dyed in the shades shown in Table 1 below; they were assessed visually.

Figure img00200002

<Tb>
<Tb>

Exempt <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4
<tb> Height <SEP> of <SEP> tone <SEP> Chestnut <SEP> Chestnut <SEP> Chestnut <SEP> Chestnut
<tb> dark <SEP> clear <SEP> dark
<tb> Reflection <SEP> Pink <SEP> Violine <SEP> Mahogany <SEP> Blue
<tb> fuchsia <SEP> iridescent <SEP> iridescent <SEP> deep
<Tb>

Claims (26)

  1.  or one of its addition salts; said composition not containing 3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole.
    Figure img00210001
     1. A dye composition comprising, in a suitable dyeing medium, at least one heterocyclic oxidation base chosen from: (i) 4,5-diamino-1- (2-hydroxyethyl) pyrazole and its addition salts; (ii) cyclic amino paraphenylenediamines and their addition salts; (iii) pyrazolo [1,5-a] pyrimidines and their addition salts; at least as a coupler, 1-N- (ss-hydroxyethyl) 4-hydroxyindole of formula:
  2. 2. The composition according to claim 1, wherein the para-phenylenediamines containing a cyclic amino group are chosen from the following paraphenylenediamine derivatives of formula (1), or their addition salts:
    Figure img00210002
     in which - Z represents the atoms necessary to form a saturated ring of 3 to 8 members, these atoms possibly being carbon or nitrogen atoms, the ring being able to be substituted,
    <Desc / Clms Page number 22>
     - R1 represents a hydrogen atom; a halogen atom selected from a chlorine and bromine atom; a linear or branched, saturated or unsaturated C 1 -C 4 hydrocarbon-based chain of which one or more carbon atoms may be replaced by an oxygen, nitrogen or sulfur atom or by an S02 group, and whose carbon atoms may to be, independently of one another, substituted by one or more halogen atoms; said radical R1 having no peroxide bond, or diazo, nitro or nitroso radicals,
  3. 3. Composition according to claim 2, wherein the oxidation base chosen from paraphenylenediamine derivatives of formula (1) is such that Z represents the carbon atoms necessary to form a saturated 5- to 8-membered ring.
  4. 4. Composition according to any one of claims 2 or 3, wherein R1 represents a hydrogen atom, an alkyl radical, an alkenyl radical, an alkynyl radical, an alkoxyalkyl radical, a hydroxyalkyl radical, an alkoxy radical, a radical. allyloxy, a hydroxyaminoalkyl radical, a hydroxyalkoxy radical, a carboxylalkyl radical, an aminoalkyl radical.
  5. 5. Composition according to claim 4, wherein R1 represents a hydrogen atom, a radical chosen from methyl, ethyl, isopropyl, vinyl,
    Figure img00220001
     allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or 2-hydroxyethyloxy
  6. 6. Composition according to claim 5, wherein R1 represents a hydrogen atom, a methyl, hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, methoxy or 2-hydroxyethoxy radical.
    <Desc / Clms Page number 23>
     in which: R 1 is as defined above, R 2 represents a hydrogen atom; a hydroxyl radical; an amino radical; a radical-OR4 in which R4 represents a C1-C4 alkyl radical substituted with one or more radicals chosen from a halogen atom, C1-C2 alkoxy, amino, C1-C2 aminoalkyl or mono-or poly-C1-4 radicals; C1-C4 hydroxyalkyl; a methylcarbonyl radical; a radical -NRsR6 in which Rs and R6 represent, independently of one another, a hydrogen atom, a C 1 -C 4 alkyl radical which may be substituted by one or more radicals chosen from a halogen atom, hydroxyl, C1-C2 alkoxy, amino or C1-C2 aminoalkyl radicals; - R3 represents a hydrogen atom; a carbamoyl radical, an amido radical; a mono-or poly-hydroxy-C 1 -C 5 radical.
    Figure img00230001
  7.  The composition according to any one of claims 2 to 6, wherein the cyclic amino paraphenylenediamines correspond to the following formula (Ia):
  8. 8. Composition according to claim 7, wherein R2 represents a hydrogen atom, a hydroxyl radical, acetoxy, amino, alkylamino, hydroxyalkylamino.
  9. 9. Composition according to claim 8, wherein R2 is a hydrogen atom, a hydroxyl, acetoxy, amino, methylamino, dimethylamino or 2 hydroxyethylamino radical.
  10. 10. Composition according to claim 9, wherein R2 represents a hydrogen atom, a hydroxyl radical or an amino radical.
    <Desc / Clms Page number 24>
    Figure img00240001
  11. 11. Composition according to any one of claims 7 to 10, wherein R3 preferably represents a hydrogen atom, a carbamoyl radical, a hydroxy radical, a C1-C4 hydroxyalkyl radical, a methyl radical.
  12. 12. Composition according to any one of claims 7 to 11, wherein the paraphenylenediamine derivatives of formula (1) are chosen from N- (4-aminophenyl) -3-hydroxy-pyrrolidine, N- (4-amino-2- methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-methoxyphenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (2-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1,2-dihydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methoxyphenyl) -3-hydroxypyrrolidine, N- (4-amine) 3- (2-hydroxy-ethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1, 2-dihydroxyethyl) phenyl) -3-hydroxy-pyrrolidine, N- (4-amino-phenyl) -3-aminopyrrolidine, N- (4-amino-2-methyl-phenyl) -3-aminopyrrolidine, N- (4-amino-phenyl) -3-hydroxy-pyrrolidine; amino-2-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-2-methoxyphenyl) -3-aminopyrrolidine, N- (4-amino-2- (2-hydroxy-ethyl) phenyl) -3- -aminopyrrolidine, N- (4-amino-2- (1hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amine) no-2- (1, 2-dihydroxyethyl) phenyl) -3-hydroxy-pyrrolidine, N- (4-amino-3-methylphenyl) -3-aminopyrrolidine, N- (4-amino-3-ethylphenyl) -3- aminopyrrolidine, N- (4-amino-3-methoxyphenyl) -3-amino-pyrrolidine, N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-3-aminopyrrolidine) amino-3- (1-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-3- (1,2-dihydroxyethyl) phenyl) -3-aminopyrrolidine, 1- (4-aminophenyl) -pyrrolidine, (4-aminophenyl) -2-pyrrolidinemethanol, 1- (4-aminophenyl) -4-hydroxy-2-pyrrolidinemethanol, N- (4-aminophenyl) -prolineamide and their addition salts.
  13. 13. Composition according to any one of claims 1 to 12, wherein the pyrazolo [1,5-a] pyrimidines are chosen from the compounds corresponding to the following formula (II), and their addition salts:
    <Desc / Clms Page number 25>
     in which: R7, R8, Rg and Rio denote, identical or different, a hydrogen atom; a C1-C4 alkyl radical; an aryl radical; a C1-C4 hydroxyalkyl radical; a C2-C4 polyhydroxyalkyl radical; a (C1-C4) alkoxy C1-C4 alkyl radical; a C1-C4 aminoalkyl radical; a C 1 -C 4 alkylamino radical whose amine is protected by an acetyl, ureido or sulfonyl radical; a (C1-C4) alkylamino (C1-C4) alkyl radical; a di- [(C1-C4) alkyl] amino C1-C4 alkyl radical in which the dialkyls can form a 5- or 6-membered aliphatic or heterocyclic ring; a hydroxy (C1-C4) alkyl- or di- [hydroxy (C1-C4) alkyl] -amino C1-C4 alkyl radical; the radicals X denote, identical or different, a hydrogen atom, a C 1 -C 4 alkyl radical, an aryl radical, a C 1 -C 4 hydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical or a C 1 -C 6 alkylamino radical; -C4, a (C1-C4) alkylamino (C1-C4) alkyl radical, a di- [(C1-C4) alkyl] amino C1-C4 alkyl radical in which the dialkyls can form an aliphatic or heterocyclic ring at 5 or 6-membered, hydroxy (C 1 -C 4) alkyl- or di- [hydroxy (C 1 -C 4) alkyl] amino C 1 -C 4 alkyl, amino, (C 1 -C 4) alkyl- or di- [( C1-C4) alkyl] amino; a halogen atom, a carboxylic acid group, or a sulfonic acid group; i is 0, 1, 2 or 3; p is 0 or 1; q is 0 or 1; n is 0 or 1; provided that: - (i) the sum p + q is different from 0; - (ii) when p + q is equal to 2, then n is 0 and the groups NR6R7 and NRgRg occupy the positions (2,3); (5.6); (6.7); (3,5) or (3,7); - (iii) when p + q is equal to 1 then n is 1 and the NR6R7 (or NRsRg) group and the OH group occupy the positions (2,3); (5.6); (6.7); (3.5) or (3.7).
    Figure img00250001
    <Desc / Clms Page number 26>
     pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2-methyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,2-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo- [1, 5-a] pyrimidin-7-ol; 3-amino-5-methyl pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-Amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) -ethanol; 3-amino-7-ss-hydroxyethylamino-5-methyl-pyrazolo [1,5-a] pyrimidine; 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol; 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5, N-7, N-7-tetramethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine; and their addition salts.
    Figure img00260001
  14.  The composition of claim 13, wherein the pyrazolo [1,5-a] pyrimidines are selected from:
  15. 15. Composition according to any one of claims 1 to 14, comprising an additional oxidation base selected from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than the defined heterocyclic bases. in claims 1 to 14; as well as their addition salts.
  16. 16. Composition according to any one of claims 1 to 15, comprising a coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers other than: 1-N- (p-hydroxyethyl) -4-hydroxy indole and their addition salts.
    <Desc / Clms Page number 27>
  17. 17. Composition according to any one of claims 1 to 16, wherein the amount of each of the oxidation bases is between 0.001 to 10% by weight of the total weight of the dye composition.
  18. 18. Composition according to any one of claims 1 to 17, wherein the amount of each of the couplers is between 0.001 and 10% by weight of the total weight of the dye composition.
  19. 19. Composition according to any one of claims 1 to 18 comprising an oxidizing agent.
  20. 20. The composition of claim 19, wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.
  21. 21. Process for the oxidation dyeing of keratin fibers, characterized in that at least one composition as defined in any one of Claims 1 to 18 is applied to the fibers, and the color is revealed using an oxidizing agent.
  22. 22. The method of claim 21, wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.
  23. 23. Method according to one of claims 21 or 22 wherein the oxidizing agent is mixed at the time of use in the composition as defined in any one of claims 1 to 18.
    <Desc / Clms Page number 28>
  24. 24. Process according to claim 21, in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the composition as defined according to any one of claims 1 to 18.
  25. 25. Multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 18 and a second compartment contains an oxidizing composition.
  26. 26. Use of the dye composition defined in claims 1 to 20 for dyeing keratinous fibers.
FR0113764A 2001-10-24 2001-10-24 Dye composition comprising at least one heterocyclic base, and 1-N- (b-hydroxyethyl) 4-hydroxyindole as coupler; dyeing processes Expired - Fee Related FR2831055B1 (en)

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FR2864957A1 (en) * 2004-01-09 2005-07-15 Oreal Dyeing composition for keratin fibers, especially human hair, containing new or known p-phenylene diamine derivative with one amine group in heptamethyleneimine form as oxidation base
WO2005068431A1 (en) * 2004-01-09 2005-07-28 L'oreal Composition for dyeing keratin fibres, comprising at least one para-phenylenediamine derivative
CN100471483C (en) 2003-06-19 2009-03-25 莱雅公司 Dyeing composition comprising oxidation coloration alkali and 6-hydroxyindole as color coupler
US8444711B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a benzene-1,3-diamine and derivatives thereof
US8444709B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a 2-aminophenol and derivatives thereof
US8444712B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a benzo[1,3]dioxol-5-ylamine and derivatives thereof
US8444713B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a naphthalen-1-ol and derivatives thereof
US8444714B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-Hexy1/Hepty1-4,5-diaminopyrazole and a benzene-1,3-diol and derivatives thereof
US8444710B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a m-aminophenol and derivatives thereof
US8460397B2 (en) 2011-02-22 2013-06-11 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a pyridine and derivatives thereof

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ES2478269T3 (en) 2012-02-16 2014-07-21 The Procter & Gamble Company Hemisulfate 1-hexyl-1H-pyrazole-4,5-diamine, and their use in compositions for dyeing

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US5609649A (en) * 1989-11-10 1997-03-11 L'oreal Tinctorial composition for keratinous fibers containing oxidation dye precursors and couplers derived from 4-hydroxyindole, and dyeing method using them
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100471483C (en) 2003-06-19 2009-03-25 莱雅公司 Dyeing composition comprising oxidation coloration alkali and 6-hydroxyindole as color coupler
FR2864957A1 (en) * 2004-01-09 2005-07-15 Oreal Dyeing composition for keratin fibers, especially human hair, containing new or known p-phenylene diamine derivative with one amine group in heptamethyleneimine form as oxidation base
WO2005068431A1 (en) * 2004-01-09 2005-07-28 L'oreal Composition for dyeing keratin fibres, comprising at least one para-phenylenediamine derivative
US8444711B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a benzene-1,3-diamine and derivatives thereof
US8444709B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a 2-aminophenol and derivatives thereof
US8444712B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a benzo[1,3]dioxol-5-ylamine and derivatives thereof
US8444713B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a naphthalen-1-ol and derivatives thereof
US8444714B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-Hexy1/Hepty1-4,5-diaminopyrazole and a benzene-1,3-diol and derivatives thereof
US8444710B2 (en) 2011-02-22 2013-05-21 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a m-aminophenol and derivatives thereof
US8460397B2 (en) 2011-02-22 2013-06-11 The Procter & Gamble Company Oxidative dyeing compositions comprising an 1-hexyl/heptyl-4,5-diaminopyrazole and a pyridine and derivatives thereof

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