FR2830193A1 - TINCTORIAL COMPOSITION COMPRISING A DIAMINOPYRAZOLE-TYPE OXIDATION BASE AND AN ENZYMATIC-TYPE OXIDIZING AGENT - Google Patents

Abstract

The invention concerns a dyeing composition comprising a diaminopyrazole oxidation base and an oxidoreductase type enzymatic oxidizing agent. The invention also concerns the use of said composition for dyeing keratinous fibres and the dyeing method using said composition.

Description

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TINCTORIAL COMPOSITION COMPRISING A DIAMINOPYRAZOLE-TYPE OXIDATION BASE AND AN ENZYMATIC-TYPE OXIDIZING AGENT
The subject of the invention is a dyeing composition comprising a diaminopyrazole-type oxidation base and an oxidizing oxidizing enzyme of the oxidoreductase type. 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.

 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.

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des compositions tinctoriales comprenant des dérivés 4, 5-diaminopyrazoles associés à des métaphénylènediamines particulières. La demande de brevet DE 19643059 décrit des compositions tinctoriales associant des dérivés 4, 5-diaminopyrazoles avec des coupleurs metaaminophénols et métaphénylènediamines. La demande de brevet DE 19646609 décrit des compositions tinctoriales associant des dérivés 4,5diaminopyrazoles avec des coupleurs benzoxazines. It is already known dye compositions comprising as base oxidation of diaminopyrazole derivatives. For example, patent application DE 3843892 describes dyeing compositions for dyeing keratinous fibers comprising 4,5-diaminopyrazole derivatives which may be substituted in the 2-position by alkyl or hydroxyalkyl radicals. Patent application EP 692245 describes

dye compositions comprising 4,5-diaminopyrazole derivatives associated with particular meta-phenylenediamines. Patent Application DE 19643059 describes dye compositions combining 4,5-diaminopyrazole derivatives with couplers metaaminophenols and metaphenylenediamines. Patent Application DE 19646609 discloses dye compositions associating 4,5diaminopyrazole derivatives with benzoxazine couplers.

 The oxidation dye of keratinous fibers is generally carried out in an alkaline medium, in the presence of an oxidizing agent, generally hydrogen peroxide. However, the use of alkaline media in the presence of hydrogen peroxide causes significant degradation of the fibers and significant discoloration of keratin fibers which is not always desirable.

 It is known to replace hydrogen peroxide with enzymatic systems. Thus, it has already been proposed to dye keratinous fibers, in particular in the patent application EP-A-0310675, with compositions comprising an oxidation base and optionally a coupler, in combination with enzymes of the oxido-reductase type. 2 electrons, such as pyranose oxidase, glucose oxidase or uricase, in the presence of a donor for said enzymes.

 It has also already been proposed, in particular in patent applications FR-A-2112549, FR-A-2694018, EP-A-0504005, WO 95/07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998, WO97 / 19999 and US Pat. No. 3251742, for dyeing keratinous fibers with compositions comprising in particular an oxidation dye precursor and a laccase enzyme (4-electron oxidoreductase).

 These dyeing processes, although being carried out under conditions that do not lead to a degradation of the keratinous fibers comparable to that caused by the dyes carried out in the presence of hydrogen peroxide,

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 lead to colorations that do not give complete satisfaction, especially from the point of view of their intensity.

 The object of the present invention is to provide novel dye compositions for dyeing keratinous fibers which do not degrade keratin fibers, while being capable of generating intense coloring in various shades, not very selective and particularly resistant.

dans laquelle R1 est un radical alkyle en Cl-C,, substitué par un ou plusieurs radicaux OR, R étant un radical alkyle en Cl-C6, et 'un agent oxydant enzymatique choisi parmi (a) un système enzymatique comprenant une oxydo-réductase à 2 électrons et un donneur pour cette oxydoréductase ou (b) une oxydo-réductase à 4 électrons. This object is achieved with the present invention which relates to a dyeing composition comprising, in a suitable dyeing medium, at least one 4,5-diaminopyrazole oxidation base of formula (1) or the corresponding addition salts:

wherein R 1 is a C 1 -C 6 alkyl radical substituted with one or more OR radicals, R is a C 1 -C 6 alkyl radical, and an enzymatic oxidizing agent selected from (a) an enzyme system comprising an oxido reductase 2-electron and a donor for this oxidoreductase or (b) a 4-electron oxidoreductase.

 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, 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, butyl, etc.

 According to one particular embodiment, the 4,5-diaminopyrazole oxidation base of formula (1) is such that R 1 represents a C 1 -C 4 alkyl radical,

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 preferably C 2 -C 4 substituted with a radical OR, R being a C 1 -C 4 alkyl radical, preferably a C 1 -C 2 alkyl radical.

 Preferably, the oxidation base of formula (1) is 4,5-diamino-1- (2'-methoxyethyl) pyrazole.

 In the composition of the present invention, the 2-electron oxidoreductase is chosen from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, uricases, choline oxidases, sarcosine oxidases, bilirubin oxidases and amino acid oxidases.

 The 2-electron oxidoreductase is preferably chosen from uricases of animal, microbiological or biotechnological origin. By way of example, mention may in particular be made of uricase extracted from wild boar liver, Arthrobacter globiformis urease, and Aspergillus flavus uricase.

 The 2-electron oxidoreductase (s) may be used in pure crystalline form or in a diluted form in an inert diluent for said 2-electron oxidoreductase.

 According to the invention, the term "donor" means the different substrates necessary for the operation of the 2-electron oxidoreductases.

sarcosine oxydases, on peut citer la sarcosine, la N-méthyl-L-leucine, la N-méthyl-DL- alanine, et la N-méthyl-DL-valine ; et enfin, à titre de donneur pour les bilirubine oxydases, on peut citer la bilirubine. The nature of the donor for said enzyme varies depending on the nature of the 2-electron oxidoreductase that is used. For example, as a donor for pyranose oxidases, there may be mentioned D-glucose, L-sorbose and D-xylose; as a donor for glucose oxidases, mention may be made of D-glucose; as a donor for glycerol oxidases, mention may be made of glycerol and dihydroxyacetone; as a donor for lactate oxidases, lactic acid and its salts may be mentioned; as a donor for pyruvate oxidases, mention may be made of pyruvic acid and its salts; as a donor for uricases, there may be mentioned uric acid and its salts; as a donor for choline oxidases, there may be mentioned choline and its addition salts with an acid such as choline hydrochloride, and betaine aldehyde; as a donor for

sarcosine oxidases include sarcosine, N-methyl-L-leucine, N-methyl-DL-alanine, and N-methyl-DL-valine; and finally, as a donor for bilirubin oxidases, there may be mentioned bilirubin.

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 The 2-electron oxidoreductase is generally from 0.01% to 20%, preferably from 0.1% to 5% by weight relative to the total weight of the dyeing composition, and the donor generally represents from 0.01% to 20% by weight. preferably from 0.1 to 5% by weight of the total weight of the dyeing composition.

 The amount of enzyme can also be defined according to its activity.

 The enzymatic activity of the 2-electron oxidoreductases useful in the present invention can be defined from the oxidation of the donor under aerobic conditions.

 A unit U corresponds to the amount of enzyme leading to the generation of a tmole of H 2 O 2 per minute at a pH of 8.5 and at a temperature of 25 ° C. Preferably, the amount of oxidoreductase with 2 electrons complies with to the invention is between 10 and 108 U units per 100 g of dye composition.

 The one or more 4-electron oxidoreductases useful in the dyeing composition of the invention may be chosen in particular from laccases, tyrosinases, catechol oxidases and polyphenol oxidases.

 According to a particular and preferred embodiment, the 4-electron oxidoreductase (s) are chosen from laccases.

 These laccases may in particular be chosen from laccases of plant origin, of animal origin, of fungal origin (yeasts, molds, fungi) or of bacterial origin, the organisms of origin possibly being mono- or multicellular.

Laccases can also be obtained by biotechnology.

 Among the laccases of plant origin, mention may be made of laccases produced by plants carrying out chlorophyll synthesis such as those indicated in the patent application FR-A-2694018. These include laccases present in extracts of Anacardiaceae such as, for example, extracts of Magnifera indica, Schinus molle or Pleiogynium timoriense; in extracts of Podocarpaceae; from Rosmarinus off. ; Solanum tuberosum; of Iris sp. ; from Coffea sp.

; of Daucus carrota; of Vinca minor; Persea americana; Catharenthus roseus; of Musa sp. ; Malus pumila; Gingko biloba; of Monotropa hypopithys (sucepin), Aesculus sp. ; Acer pseudoplatanus; of Prunus persica and Pistacia palaestina.

 Among the laccases of fungal origin, possibly obtained by biotechnology, mention may be made of the laccase (s) derived from Polyporus versicolor,

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 Rhizoctonia praticola and Rhus vernicifera as described for example in patent applications FR-A-2 112 549 and EP-A-504005; the laccases described in the patent applications WO95 / 07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998 and WO97 / 19999, such as for example the laccase (s) derived from Scytalidium, Polyporus pinsitus, Myceliophtora thermophila , Rhizoctonia solani, Pyricularia orizae, and their variants. Laccase (s) from Trametes versicolor, Fomes fomentarius, Chaetomium thermophilus, Neurospora crassa, Colorius versicol, Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans, may also be mentioned. Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrestris, Cladosporium cladosporioides, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermispora, of Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squales, and their variants.

 More preferably, laccases of fungal origin, possibly obtained by biotechnology, will be chosen.

 The enzymatic activity of laccases can be defined from the oxidation of syringaldazine under aerobic conditions. The Lacu unit corresponds to the amount of enzyme catalyzing the conversion of 1 mmol of syringaldazine per minute at a pH of 5.5 and at a temperature of 30 ° C. The unit U corresponds to the amount of enzyme producing a delta absorbance of 0.001 per minute, at a wavelength of 530 nm, using syringaldazine as a substrate at 30 C and a pH of 6.5. The enzymatic activity of the laccases used according to the invention can also be defined from the oxidation of para-phenylenediamine. The ulac unit corresponds to the amount of enzyme producing an absorbance delta of 0.001 per minute, at a wavelength of 496.5 nm, using paraphenylenediamine as substrate (64 mM), at 300C and at a pH of 5.

 In general, the one or more 4-electron oxidoreductases represent from 0.01 to 20% by weight approximately of the total weight of the dye composition, and preferably from 0.1 to 5% by weight approximately of this weight.

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 In particular, and when one or more laccases are used, the amount of laccase (s) present in the dye composition according to the invention varies depending on the nature of the laccase (s) used. Preferably, the amount of laccase (s) is between about 0.5 and 2000 Lacu (or between about 10000 and 40, 106 units U or between 20 and 20. 106 ulac units) per 100 g of dye composition.

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 additional oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than those previously described and their addition salts.

2-hydroxyméthyl paraphénylènediamine, la N, N-diméthyl 3-méthyl paraphénylènediamine, la N, N- (éthyl, ss-hydroxyéthyl) paraphénylènediamine, la N- (ss, ydihydroxypropyl) paraphénylènediamine, la N- (4'-aminophényl) paraphénylènediamine, la N-phényl paraphénylènediamine, la 2-ss-hydroxyéthyloxy paraphénylènediamine, la 2-ss-acétylaminoéthyloxy paraphénylènediamine, la N-(ss-méthoxyéthyl) paraphénylènediamine, la 4-aminophénylpyrrolidine, la 2-thiényl paraphénylènediamine, le 2-ss hydroxyéthylamino 5-amino toluène, la 3-hydroxy 1- (4'-aminophényl) pyrrolidine et leurs sels d'addition avec un acide. 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- (5-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (ss-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (p-hydroxyethyl) amino 2-chloroaniline, 2 p-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (p-hydroxypropyl) -paraphenyl) -enediamine,

2-hydroxymethyl paraphenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, s-hydroxyethyl) paraphenylenediamine, N- (ss, dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) para-phenylenediamine N-phenyl-para-phenylenediamine, 2-ss-hydroxyethyloxy-para-phenylenediamine, 2-ss-acetylaminoethyloxy-para-phenylenediamine, N- (ss-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2-ss-hydroxyethylamino amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

 Among the para-phenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine,

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 2-ss-hydroxyethyl paraphenylenediamine, 2-ss-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- ( Β-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-ss-acetylaminoethyloxy-para-phenylenediamine, and acid-addition salts thereof are particularly preferred.

aminophényl) tétraméthylènediamine, la N, N'-bis- {4-méthyl-aminophényl) tétraméthylènediamine, la N, N'-bis-(éthyl) N, N'-bis- {4'-amino, 3'-méthylphényl) éthylènediamine, le 1, 8-bis-(2,5-diamino phénoxy)-3, 6-dioxaoctane, et leurs sels d'addition avec un acide. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (β-hydroxyethyl) N, N'-bis (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (ss) 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 their addition salts with an acid.

 Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplified. methyl phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (ss-hydroxyethylaminomethyl) phenol, 4-amino-2 -fluor phenol, and their addition salts with an acid.

 Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts with an acid.

 Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

 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-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2- (ss-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

 Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts

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amino-pyrazolo[1, 5-a]pyridin-2-carboxylique ; la 2-méthoxy-pyrazolo[1, 5-a]pyridine-3ylamino ; le (3-amino-pyrazolo [1, 5-a] pyridine-7-yl)-méthanol ; le 2- (3-aminopyrazolo[1, 5-a]pyridine-5-yl) -éthanol ; le 2- (3-amino-pyrazolo[1, 5-a]pyridine-7 -yl) - éthanol ; le (3-amino-pyrazolo[1, 5-a]pyridine-2-yl) -méthanol ; la 3, 6-diaminopyrazolo[1, 5-a]pyridine ; la 3, 4-diamino-pyrazolo[1, 5-a]pyridine ; la pyrazolo[1, 5a]pyridine-3, 7 -diamine ; la 7 -morpholin-4-yl-pyrazolo[1, 5-a]pyridin-3-ylamine ; la pyrazolo[1, 5-a]pyridine-3, 5-diamine ; la 5-morpholin-4-yl-pyrazolo[1, 5-a]pyridin-3- ylamine ; le2- [ (3-amino-pyrazolo [1, 5-a] pyridin-5-yl)- (2-hydroxyéthyl)-amino]-éthanol ;

le 2- [ (3-amino-pyrazolo [1, 5-a] pyridin-7-yl)- (2-hydroxyéthyl)-amino]-éthanol ; la 3amino-pyrazolo[1, 5-a]pyridine-5-ol ; 3-amino-pyrazolo[1, 5-a]pyridine-4-ol ; la 3amino-pyrazolo[1, 5-a]pyridine-6-ol ; la 3-amino-pyrazolo[1, 5-a]pyridine-7-ol ; ainsi que leurs d'addition avec un acide ou avec une base. for example, pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3- acid

amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridine-3-ylamino; (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-aminopyrazolo [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-diaminopyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5a] 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-amino-pyrazolo [1,5-a] pyridin-5-ol; 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 with an acid or with a base.

2- (3-amino pyrazolo- [1, 5-a]-pyrimidin-7-ylamino)-éthanol, le 2- (7-amino pyrazolo- [1, 5a]-pyrimidin-3-ylamino) -éthanol, le 2-[ (3-amino-pyrazolo[1, 5-a]pyrimidin-7 -yl) - (2-hydroxy-éthyl) -amino]-éthanol, le 2-[ (7 -amino-pyrazolo[1, 5-a]pyrimidin-3-yl) - (2-hydroxy-éthyl) -amino]-éthanol, la 5, 6-diméthyl pyrazolo-[1, 5-a]-pyrimidine- 3, 7-diamine, la 2, 6-diméthyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, la 2,5, N 7, N 7tetraméthyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, la 3-amino-5-méthyl-7- 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 2,5,6-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 the patent application FR-A-2750048 and among which mention may be made of pyrazolo [1, 5-a] -pyrimidine-3, 7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-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 pyrazolo [1,5-a] pyrimidin-5-ol; the

2- (3-Amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) -ethanol, 2- (7-Amino-pyrazolo [1,5a] -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-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2, 6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5, N, N, 7-tetramethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 3-amino-5-methyl-7-

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 imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their addition salts with an acid and their tautomeric forms, when tautomeric equilibrium exists.

pyrazol, le 4-amino 5- (2'-aminoéthyl} amino 1, 3-diméthyl pyrazol, le 3, 4, 5-triamino pyrazol, le 1-méthyl 3, 4, 5-triamino pyrazole, le 3, 5-diamino 1-méthyl 4-méthylamino pyrazol, le 3, 5-diamino 4- (P-hydroxyéthyl) amino 1-méthyl pyrazol, et leurs sels d'addition avec un acide. 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 diamino 1-methyl pyrazol, 4,5-diamino 1- (p-hydroxyethyl) pyrazo) e) 3,4-diamino pyrazole, 4,5diamino 1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazol, 4,5-diamino-1-tert-butyl-3-methyl-pyrazol, 4 5-diamino 1- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, diamino-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'-aminoethyl) amino-1,3-dimethyl-pyrazole, 3,4,5-triamino-pyrazol, 1-methyl-3,4,5-triamino-pyrazole, 3,5-triamino-pyrazole, diamino 1-methyl-4-methylamino pyrazol, 3,5-diamino 4- (P-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with an acid.

 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%.

aminophénols, les métadiphénols, les coupleurs naphtaléniques, les coupleurs hétérocycliques et leur sels d'addition. The composition according to the invention may contain one or more 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 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- (ss-hydroxethyloxy) benzene, 2-amino-4 (-s-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene,

<Desc / Clms Page number 11>

 sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (ss-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2, 6-bis (ss-hydroxyethylamino) toluene and their addition salts with an acid.

 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 dye 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.

 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.

comme le 2-butoxyéthanol, le propylèneglycol, le monométhyléther de propylèneglycol, le monoéthyléther et le monométhyléther du diéthylèneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, et leurs mélanges. 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. Examples of organic solvents that may be mentioned are lower C1-C4 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.

<Desc / Clms Page number 12>

 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.

 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 (II):

<Desc / Clms Page number 13>

dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en Cl-C4 ; Ra, Rb, Rc et Rd, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 ou hydroxyalkyl en C1-C4.

wherein W is a propylene residue 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, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair.

 In the dyeing composition according to the invention, the oxidation bases and the 2-electron or 4-electron oxidoreductase (s) are present within the same composition, and consequently the composition, if it is stored before use, must be free from gaseous oxygen, so as to avoid any premature oxidation of the oxidation dye (s).

 The invention also relates to a process for dyeing keratinous fibers and in particular human keratinous fibers such as the hair using the dye composition as defined above.

 According to this method, the dye composition as defined above is applied to the fibers for a time sufficient to develop the desired coloration. Preferably, the fibers are then rinsed, optionally washed with shampoo, and then dried.

 The application temperature is preferably between room temperature and 600C and even more preferably between 350C and 50C.

 The time sufficient to develop the coloration on the keratinous fibers is generally between 1 and 60 minutes and preferably between 5 and 30 minutes.

 Another object of the invention is a multi-compartment device in which a first compartment contains a dye composition comprising an oxidation base of formula (1) and a second compartment contains an enzymatic oxidizing agent as defined above. These devices can be

<Desc / Clms Page number 14>

 equipped with a means for delivering the desired mixture onto 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 comprising at least one oxidation base of formula (1) with an enzymatic oxidizing agent as defined previously, and the application of the mixture obtained on the keratinous fibers for a time sufficient to develop the desired coloration.

 The compounds useful in the composition of the present invention are known compounds which can be obtained from general preparation methods known to those skilled in the art. For example, the synthetic approach shown below is described in the literature up to intermediate (2) (J.

Juffermanns, C. L .; Habraken; J. Org. Chem., 1986, 51, 4656; Klebe et al. ; Synthesis, 1973,294; R. Hüttel, F. Büchele; Chem. Ber. ; 1955, 88, 1586.). In the present case, the passage of compound 3 to compound 2 is carried out using an NH 3 / EtOH mixture.

The alkylation and amination to arrive at the compounds of formula (1) according to the invention are mentioned in DE 42 34 885.

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

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EXAMPLES Example 1. Synthesis of 4,5-Diamino-1- (2'-methoxyethyl) pyrazole dihydrochloride

A mixture of 5-benzylamino-3-bromo-1- (2'-methoxyethyl) -4-nitropyrazole (4 g, 2.8 mmol) in ethanol (500 ml) containing a 10% Pd / C catalyst ( Johnson-Mattey Type 487, dry weight 0.5 g) and 36% hydrochloric acid (0.57 g, 5.6 mmol) is hydrogenated in a Parr Autoclave (11) at 1 MPa for 1 h. The catalyst is then removed by filtration, washed with ethanol and the filtrate evaporated under reduced pressure. This gives a crude orange solid (2.8 g) which has been triturated in AcOEt (20 ml) for 1 h. The solid is then filtered and washed with cold AcOEt (20 ml) and then dried under vacuum in order to give 4,4-diamino-1- (2'-methoxyethyl) pyrazole in the form of a beige solid (0.7 g , 27%).

HPLC (purity): 99.5%
Mp: 168, 1-173, 0 C NMR: 1H (400 MHz, d6-DMSO): 7.34 (1H, s, NH), 5.18 (1H, broad, NH), 4.09 ( 2H, t, J = 5.5Hz, CH2N), 3.61 (2H, t, J = 5.5Hz, CH2O), 3.23 (3H, s, OCH3).

EXAMPLE 2 Dye Composition Containing 4,5-Diamino-1- (2'-methoxyethyl) -pyrazole Dihydrochloride The following dye composition was prepared:

<Tb>
<tb> 4, <SEP> 5-Diamino-1- (2'-methoxyethyl) -pyrazole, <SEP> 2HCl <SEP> 0.744
<tb> 2-methyl-5-am <SEP> ino-phenol <SEP> 0.39 <SEP> g
<tb> N-acetyl-L-cysteine <SEP> 0, <SEP> 10 <SEP> g
<tb> Uricase <SEP> 20. <SEP> 103 <SEP> UnitsU
<tb> Acid <SEP> uric <SEP> 1 <SEP> 9
<tb> Monooleate <SEP> of <SEP> polyglycerol <SEP> to <SEP> 10 <SEP> moles <SEP> of <SEP> glycerol <SEP> 1 <SEP> g
<tb> Aculyn <SEP> 22 <SEP> (Rohm <SEP> and <SEP> Haas) <SEP> 0.75 <SEP> g <SEP> MA *
<tb> 2-amino-2-methyl-1-propanol. <SEP> q. <SEP> s. <SEP> p. <SEP> pH <SEP> 9.5
<tb> Demineralized <SEP> Water <SEP> q. <SEP> s. <SEP> p ...... <SEP> 100 <SEP> g
<Tb>
* means Active Matter
U: unit (amount of uricase which oxidizes a umo) of uric acid per minute at 25 ° C. and at pH 8.5 in a borate buffer)

<Desc / Clms Page number 16>

The mixture is applied to gray hair with 90% white, permed or not, at a rate of 10g for 19 of hair. After 30 min. laying, the hair is then rinsed, washed with a standard shampoo, rinsed again and dried.

 Capillary staining is evaluated visually. The reflection on wick is an intense coppery red.

Claims (22)

A dye composition comprising, in a suitable dyeing medium, at least one 4,5-diaminopyrazole oxidation base of formula (1) or the corresponding addition salts:

 in which R 1 is a C 1 -C 6 alkyl radical substituted with one or more OR radicals, R being a C 1 -C 6 alkyl radical, and an enzymatic oxidizing agent selected from (a) an enzymatic system comprising a 2-oxido reductase electrons and a donor for this oxidoreductase or (b) a 4-electron oxidoreductase.  2. Composition according to claim 1 wherein the oxidation base of formula (1) is such that R1 represents a C1-C4 alkyl radical substituted with an OR radical, R being a C1-C4 alkyl radical.  3. Composition according to claim 2 wherein the oxidation base of formula (1) is 4,5-diamino-1- (2'-methoxyethyl) pyrazole.  4. Composition according to any one of claims 1 to 3 wherein the 2-electron oxidoreductase is chosen from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, uricases, choline oxidases, sarcosine oxidases, bilirubin oxidases and amino acid oxidases.  5. Composition according to claim 1 or 4 wherein the enzymatic system comprising a 2-electron oxidoreductase and a donor for this 2-electron oxidoreductase is chosen from the following oxidoreductase / donor systems: pyranose oxidase / D -glucose, L-sorbose and D-xylose; glucose oxidase / D-glucose; glycerol oxidases / glycerol and dihydroxyacetone; <Desc / Clms Page number 18>  - lactate oxidases! lactic acid and its salts; pyruvate oxidases / pyruvic acid and its salts; - uricases / uric acid and its salts; - choline oxidases! choline and its salts; - sarcosine oxidases! sarcosine, N-methyl-L-leucine, N-methyl-DL-alanine, and N-methyl-DL-valine; - bilirubin oxidases! bilirubin.  6. Composition according to any one of claims 1 to 3 wherein the 4-electron oxidoreductase is chosen from laccases, tyrosinases, catechol oxidases and polyphenol oxidases.  7. The composition according to claim 6, in which the 4-electron oxidoreductase is a laccase chosen from laccases of plant origin, of animal origin, of fungal origin or of bacterial origin, and from laccases obtained by biotechnology. .  8. The composition of claim 7 wherein the laccase is of plant origin and selected from laccases present in the extracts of Anacardiaceae; Podocarpaceae; from Rosmarinus off. ; Solanum tuberosum; of Iris sp. ; from Coffea sp. ; of Daucus carrota; of Vinca minor; Persea americana; Catharenthus roseus; of Musa sp. ; Malus pumila; Gingko biloba; of Monotropa hypopithys (sucepin), Aesculus sp. ; Acer pseudoplatanus; of Prunus persica and Pistacia palaestina.  9. The composition of claim 7 wherein the laccase is of fungal origin or obtained by biotechnology.  10. A composition according to claim 9 wherein the laccase is selected from laccases from Polyporus versicolor, Rhizoctonia praticola, Rhus vernicifera, Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, Trametes versicolor, Fomes fomentarius, thermophilic Chaetomium, Neurospora crassa, Colorius versicol, Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans, Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrestris, Cladosporium <Desc / Clms Page number 19>  cladosporioides, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and their variants.  11. Composition according to any one of claims 1 to 5 wherein the 2-electron oxidoreductase represents from 0.01 to 20% by weight of the total weight of the dye composition and the donor represents from 0.01 to 20 % by weight of the total weight of the dye composition.  12. Composition according to any one of claims 1,6 to 10 wherein the 4-electron oxidoreductase represents from 0.01 to 20% by weight of the total weight of the dye composition.  13. Composition according to any one of the preceding claims comprising an additional oxidation base chosen from

 paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than the oxidation bases of formula (1) and their addition salts.  14. Composition according to any one of the preceding claims, comprising a coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.  15. Composition according to any one of the preceding claims wherein the amount of each of the oxidation bases is between 0.001 to 10% by weight approximately of the total weight of the dyeing composition.  16. The composition of claim 14 wherein the amount of each of the couplers is between 0.001 and 10% by weight of the total weight of the dye composition.  17. Process for the oxidation dyeing of keratin fibers, characterized in that a dye composition as defined in any one of Claims 1 to 16 is applied to the fibers for a time sufficient to develop the desired coloration.  18. The method of claim 17 wherein the composition is applied at a temperature between room temperature and 60 C. <Desc / Clms Page number 20>  19. The method of claim 17 or 18 wherein the time sufficient to develop the color is between 1 and 60 minutes.  20. A process for dyeing keratin fibers which comprises: mixing a dyeing composition comprising at least one oxidation base as defined in claims 1 to 3 with an enzymatic oxidizing agent as defined in claims 1 to 12, and applying the resulting mixture to the keratinous fibers for a time sufficient to develop the desired color.  21. A multi-compartment device in which a first compartment contains a dye composition comprising an oxidation base as defined in any one of claims 1 to 3 and a second compartment contains an enzymatic oxidizing agent as defined in claims 1, 4 to 12.  22. Use of the composition defined in claims 1 to 16 for dyeing keratinous fibers.