MXPA97010379A - Dye compositions of keratinic fibers containing pirazolo- [1,5-a] -pirimidine derivatives, dyeing procedure, new derivatives of pirazolo- [1,5-a] -pirimidine and its preparation procedure - Google Patents

Abstract

The subject of the invention is novel compositions for the oxidation reaction of keratin fibers comprising at least one particular pyrazolo- [1,5-a] -pyrimidine derivative, the dyeing process employing this composition, new pyrazolo derivatives [1]. 5-a] pyrimidine as well as its preparation procedure

Description

Oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, by an oxidative condensation process, to colored compounds and dyes. It is also known that the shades obtained with these oxidation bases can be varied by associating them with copulators or color modifiers, the latter being chosen mainly among the aromatic meta-diamines, the metaminophenols, the meta-diphenols and certain heterocyclic compounds. The variety of molecules put into play at the level of the bases of oxidation and of the couplers, allows obtaining a rich range of colors. The coloration called "permanent" obtained thanks to these dyes by oxidation, must on the other hand satisfy a certain number of demands. Therefore, it should not have toxicological drawbacks, it should allow obtaining tonalities in the desired intensity, present a good behavior in front of external agents (light, washing weather, permanent wave, perspiration, friction).

The dyes must also make it possible to cover the white hairs, and lastly, to be as non-selective as possible, that is, to obtain the smallest possible differences in coloration along the same keratin fiber, which may be differently sensitized ( that is, spoiled) between its tip and its root. They must also present a good chemical stability in the formulations. They must have a good toxicological profile. It has already been proposed, mainly in patent application DE 4 029 324, to use certain pyrazolo- [1, 5-a] -pyrimidine derivatives, which may be substituted by C 4 -C 4 alkyl radicals in position 4,5 and / or 6, as couplers for dye by oxidation of keratin fibers. It has also been proposed in patent application DE 4 133 957 to use certain pyrazolo [1, 5-a] -pyrimidine derivatives belonging to the family of tetrahydro pyrazolo [1,5-a] -pyrimidines as dye precursors by oxidation for dye by oxidation of keratin fibers. The applicant has now discovered, quite unexpectedly and surprisingly, a new family of pyrazolo [1, 5-a] -pyrimidine derivatives of formula (I) defined above, partly new in themselves, which can be converted for as dye precursors by oxidation, but which also allow to obtain dyeing compositions that lead to strong colorations and that have a good behavior against external agents (light, weathering, washing, permanent waving, perspiration, rubbing). Finally, it has been found that these compounds can be easily synthesized and are chemically stable. They present a good toxicological profile. These discoveries form the basis of the present invention.

DEVELOPMENT OF THE INVENTION The invention therefore has as its first object a composition for oxidation dyeing of keratin fibers and in particular of human keratin fibers such as hair, characterized in that it comprises, in an appropriate medium for dyeing , at least one pyrazolo [1,5-a] -pyrimidine derivative of the formula (I) given below as an oxidation base and / or one of its addition salts with an acid or a base and / or a of its tautomeric forms, when there is a tautomeric equilibrium: wherein: Ri, R2, R3, and R denote, identical or different, a hydrogen atom, an alkyl radical of C? -C4, an aryl radical, a hydroxyalkyl radical of C? -C4, a polyhydroxyalkyl radical of C2-C4, a (C? -C) alkoxy C? -C alkyl radical, an amino C? -C4 alkyl radical (the amine being protected by an acetyl, a ureide, a sulfonyl), a radical (C) ? -C4) C 1 -C 4 alkyl amino alkyl, a di- [(C 1 -C 4) alkyl] amino] C 1 -C 4 alkyl radical (the dialkyls can form an aliphatic or heterocyclic cycle of 5 or 6 links), a hydroxy radical (C1-C4) alkyl- or di- [hydroxy (Ci-C4) alkyl] -amino C1-C4 alkyl; - the radicals X designate, identical or different, a hydrogen atom, an alkyl radical of C? -C4, an aryl radical, a hydroxyalkyl radical of C1-C4, a polyhydroxyalkyl radical of C2-C4, an amino alkyl radical of C1 -C4, a (C1-C4) alkyl-amino-C1-C4 alkyl radical, a di- [(C1-C4) alkyl] amino-C1-C4 alkyl radical (the dialkyls being able to form an aliphatic or heterocyclic cycle of 5 or 6) links), a hydroxy radical (C 1 -C 4) alkyl or di- [hydroxy (C 1 -C 4) alkyl] amino C 1 -C 4 alkyl, an amino radical, a radical (C 1 -C 4) alkyl- or di- [( C1-C4) alkyl] -amino; a halogen atom, a carboxylic acid group, a sulfonic acid group; - i equals 0, 1, 2 or 3; - p equals 0 or 1 - q equals 0 or 1 - n equals 0 or 1; with the proviso that: - (i) the sum of p + q is different from 0; - (ii) when p + q equals 2, then n equals 0 and the groups NR? R2 and NR3R4 occupy the positions (2,3); (5,6); (6,7); (3.5); or (3,7); - (iii) when p + q equals 1, then n equals 1 and the group NR? R2 (or NR3R) and the group OH occupy the positions (2,3); (5,6); (6,7); (3.5); or (3,7).

When the compounds of the formula (I) are such that they comprise an OH group in one of positions 2, 5 or 7 in a of a nitrogen atom, there exists a tautomeric equilibrium represented for example by the following scheme: In a general manner, the addition salts with an acid which can be used in the context of the dyeing compositions of the invention (oxidation bases and couplers) are chosen mainly from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates. The addition salts with a base which can be used in the context of the dyeing compositions of the invention (oxidation bases and coupling agents) are mainly those obtained with soda, potash, ammonia or amines. Among the pyrazolo- [1, 5-a] -pyrimidine derivatives of the formula (I), which can be used as oxidation base in the compositions according to the invention, mention may be made in particular of: - pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine; - 2-methyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; - 2,5-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; - pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; - 2,7-dimethylpyrazolo- [1,5-a] -pyrimidine-3,5-diamine; - 3-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-β-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-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; - 2,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2,5, N-7, N-7-tetramethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; and its addition salts and tautomeric forms, when there is a tautomeric equilibrium. The pyrazolo- [1, 5-a] -pyrimidine derivatives of the invention of formula (I) can be prepared according to methods known and described in the literature. Reference may be made by way of examples to the following references: The pyrazolo- [1, 5-a] -pyrimidine derivatives of the invention of the formula (I) can be prepared by delation from an aminopyrazole according to the syntheses described in the following references: - EP 628559 BEIERSDORF-LILLY - R. Vishdu, H. Navedul, Indian J. Chem., 34b (6), 514, - N.S. Ibrahim, K.U. Sadek, F.A. Abdel-Al, Arch. Pharm., 320, 240, 1987. R.H. Springer, M.B. Scholten, D.E. O'Brien, T. Novinson, J.P. Miller, R.K. Robins, J. Med. Chem., 5 25,235, 1982. - T. Novinson, R.K. Robins, T.R. Matthewes, J. Med. Chem., 20, 296, 1997. - US 3907799 ICN PHARMACEUTIC S The pyrazolo- [1-2-a] -pyrimidine derivatives of the formula (I) of the invention can be prepared by delation to from hydrazine according to the syntheses described in the following references: - A. McKillop and RJ Kobilecki, Heterocycles, 6 (9), 1355, 1977. _15_ - E. Alcade, J. De Mendoza, J.M. Marcia-Marquina, C. Almera, J. Elguero, J. Heterocyclic Chem., 11 (3), 423, 1974. - K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull. Chem. Soc. Japan, 47 (2), 476, 1974. 20 By way of illustration, the 3-amino pyrazolo- [1, 5-a] -pyrimidine derivatives of formula (I) of the invention can be prepared, example, following the procedure described in scheme 1.

Scheme 1 4-Nitro-2H-pyrazol-3-ylamine hydrochloride (III) (prepared according to H. Dorn and H. Dilcher, Liebigs Ann. Chem., 707, 141, 1967) can be cyclized in preference to a derivative of acrylonitrile (IV) (Z = MeO, EtO or Me2N) or of an acrylate (V) (Z = MeO, EtO or Me2N; R '= Ci-C4 alkyl, aryl) to lead to pyrazole [1, 5] -a] pyrimines of structure (VI) (Y = NH2, OH). This reaction can be carried out based on the method of G. Mühmel, R.

Hanke and E. Breitmaier described in Synthesis, 673, 1982. The list of derivatives that can be cyclized with 4-nitro-2H-pyrazol-3-ylamine (III) is not limited to the only acrylonitrile and acrylate derivatives. Mention may be made, for example, of the β-ketoester derivatives (VIII) (X has the same definition as for the X of the preceding formula (I), R '= C 1 -C 4 alkyl, aryl), of β-keto nitrile (IX) (X has the same definition as those of the preceding formula (I)) or even of β-cyano acetal (X) (R '= C1-C4 alkyl) without being limiting. vm ?? The pyrazolo- [1, 5-a] -pyrimidines of structure (VI) can then be reduced according to known procedures (R. Hemmer, W. Lürken, in Houben-Weyl, "Methoden der Organischen Chemie", volume E16d, pages 815 et seq.). It will be preferred to use metals such as palladium (Pd), platinum (Pt) or nickel (Ni) in the presence of a hydrogen donor such as ammonium formate, formic acid or even cyclohexene instead of hydrogen (S. Ram , RE Ehrenkaufer, Synthesis, 91, 1988). Metals such as zinc (ZN), tin (Sn) or iron (Fe) may also be used in an acidic medium such as aqueous hydrochloric acid or aqueous acetic acid, optionally with the addition of an organic solvent known as methanol, Ethanol, or tetrahydrofuran. The pyrazolo- [1, 5-a] -pyrimidine derivative of formula (I) above indicated preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably of this weight . The appropriate medium for the dye (or support) is generally constituted by water or by a mixture of water and at least one organic solvent to solubilize the compounds that are not sufficiently soluble in water. As the organic solvent, there may be mentioned, for example, the lower alkanols of d-C4, such as ethanol and isopropanol; glycerol; glycols and ethers of glycols such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and mixtures thereof. The solvents can be present in proportions preferably comprised between 1 and 40% by weight approximately in relation to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately. The pH of the dye composition according to the invention is generally between about 3 and about 12, and preferably between about 5 and about 11. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in dyeing the keratin fibers or even with the aid of conventional buffer systems. Among the acidulating agents, mention may be made, by way of example, of the mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, lactic acid, acids sulphonic Among alkalizing agents, mention may be made, by way of example, of ammonia, alkali metal carbonates, alkolamines such as mono-, di-, and triethanolamines, and their derivatives, sodium or potassium hydroxides and the compounds of the following formula (II): R5 \ N - - W - - N (II) R6 ^ ^ R8 wherein W is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical of C? -C4; Rs, Re, R7 and Rs identical or different represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroalkyl radical. The dye composition according to the invention can still contain, in addition to the dyes defined above, at least one additional oxidation base which can be chosen from the oxidation bases conventionally used in oxidation dye and among which mention may be made principally of paraphenylenediamines., bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases other than the pyrazolo- [1, 5-a] -pyrimidine derivatives of the formula (I) used according to the invention. Among the para-phenylenediamines, para-phenylenediamine, para-tolylenediamine, 2,6-dimethyl para-phenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-n-propyl para-phenylenediamines, 2-isopropyl para-phenylenediamine, can be mentioned more particularly by way of example. N- (β-hydroxypropyl) paraphenylenediamine, N, -bis- (β-hydroxyethyl) paraphenylenediamine, 4-amino N- (β-methoxyethyl) aniline, paraphenylenediamines described in French patent application FR 2 630 438, and its addition salts. Among the bis-phenylalkylenediamines, m may be mentioned. { particularly, by way of example, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) -1,3-diamino propanol, N, N'-bis- (β-) hydroxyethyl) N, '-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-amino phenyl) tetramethylenediamine, N, N'-bis- (b-hydroxyethyl) N, N'- bis- (4-aminophenyl) -tetramethylenediamines, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3 ' -methylphenyl) ethylenediamine, and its addition salts. Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, can be mentioned more particularly by way of example. 4-amino-2-methyl phenol, 4-amino-2-hydroxymethyl phenol, 4-amino-2-methoxymethyl phenol, 4-amino-2-aminomethyl phenol, 4-amino-2- (β-hydroxyethyl aminomethyl) phenol, and its addition salts. Among the ortho-aminophenols, mention may be made more particularly, by way of example, of 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol, and its addition salts. Among the heterocyclic bases, mention may be more particularly made, by way of example, of pyridine derivatives, pyrimidimic derivatives, pyrazole derivatives other than the pyrazolo- [1,5-a] -pyrimidine derivatives of the formula (I) used in accordance with the invention, and its addition salts. When used, these additional oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.0005 to 6% by weight approximately of this weight. The oxidation dye compositions according to the invention can also include at least one copulator and / or at least one direct dye mainly to modify the tones or enrich them with reflections. The copulators which can be used in the oxidation dye compositions according to the invention can be chosen from the couplers conventionally used in oxidation dye and among which may be mentioned in particular metaphenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers. such as, for example, indole derivatives and their addition salts. The couplers can be chosen more particularly from 2-methyl-5-amino phenol, 5-N- (β-hydroxyethyl) amino-2-methyl phenol, 3-amino phenol, 1,3-dihydroxy benzene, 1, 3-Dihydroxy-2-methyl benzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino, 1- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethyl) amino 1-methoxy benzene, 1,3-diamino benzene, 1,3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, a-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, and their addition salts. When present, these copuladres preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately of this weight. The dyeing composition according to the invention can also include various adjuvants conventionally used in the dyeing compositions of the hair, such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or their mixtures, anionic, cationic, non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, silicones, smoke-killing agents, preservatives, pacifying agents.

Of course, the technician will take care to choose this or these additional complementary compounds in such a way that the advantageous properties intrinsically associated with the oxidation dye composition according to the invention are not, or substantially, altered by the addition (s) considered. The dye composition according to the invention can be present in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and preferably human hair.

The subject of the invention is also a dyeing process for keratin fibers and in particular for human keratin fibers such as hair using the dyeing composition as defined above. According to this method, at least one dyeing composition as defined above is applied to the fibers for a sufficient time to develop the desired coloration, either in the air, or with the help of an oxidizing agent. The dyeing composition may optionally contain oxidation catalysts, in order to accelerate the oxidation process. According to a first embodiment of the process of the invention, the coloration of fibers can be carried out without the addition of an agent, with the sole contact of oxygen in the air. According to a second embodiment of the process of the invention, at least one dye composition as defined above is applied to the fibers, the color being revealed at an acid, neutral or alkaline pH with the aid of an oxidizing agent which is added at the time of use of the dye composition or that is present in an oxidizing composition applied simultaneously or sequentially separately. According to this second embodiment of the dyeing process of the invention, the dyeing composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in a sufficient amount to develop a coloration. The mixture obtained is then applied to the keratin fibers and left to stand for about 3 to 50 minutes, preferably about 5 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried. The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for dyeing by oxidation of the keratin fibers, and among which may be mentioned hydrogen peroxide, urea peroxide, bromates of alkali metals, persalts such as perborates and persulfates. Hydrogen peroxide is particularly preferred. The pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dyeing composition, the pH of the resulting composition applied to the keratin fibers varies preferably between about 3 and about 12, and even more. preferably between 5 and 11. It is adjusted to the desired value by means of acidulating or alkalizing agents usually used in the dyeing of keratin fibers and as defined above. The oxidizing composition as defined above may also include various adjuvants conventionally used in hair dyeing compositions and as defined above. The composition that is finally applied on the keratin fibers can be presented in various forms, such as in the form of liquids, creams, gels, or in any form suitable for dyeing keratin fibers, and mainly human hair. Another object of the invention is a device with several compartments or "kit" of dye or any other system of conditioning of several compartments, whose first compartment includes the dye composition as defined above and a second compartment that includes the oxidizing composition as defined above. These devices can be equipped with a means for dispensing the desired mixture on the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. Certain compounds of the formula (I), used as the oxidation base in the context of the present invention, are new and, in this respect, constitute another object of the invention. These novel pyrazolo- [1, 5-a] -pyrimidine derivatives, their addition salts with an acid or a base and their tautomeric forms when there is a tautomeric equilibrium corresponding to the following formula (I '): wherein the radicals Ri, R2, R3, X, i-, n, p and q have the same meanings as those indicated above in formula (I), with the exception of the following compounds: __ The pyrazolo- [1, 5 α] -pyrimidine-6,7-diamine; I 5,6-Dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; I 2,6-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; I 2,5, N7, N7-tetramethyl pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine; B 2,3-dimethylpyrazolo- [1,5-a] -pyrimidine-6,7-diamine; B 6-amino-5-methyl-pyrazolo- [1, 5-a] -pyrimidin-7-ol; B 2,5-Dimethyl-6-phenyl- [1, 5-a] -pyrimidine-3,7-diamine; B 2,6-Dimethyl-5-benzyl- [1,5-a] -pyrimidine-3,7-diamine; and its addition salts. Among the novel compounds of formula (I '), mention may be made in particular: B Pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; B 2-Methyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; B 2,5-Dimethylpyrazolo- [1,5-a] -pyrimidine-3, -diamine; B Pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; B 2,7-Dimethylpyrazolo- [1,5-a] -pyrimidine-3,5-diamine; Bel 3-amino pyrazolo- [1, 5-a] -pyrimidin-7-ol; B 3-amino-5-methyl-pyrazolo- [1, 5-a] -pyrimidin-7-ol; Bel 3-amino pyrazolo- [1, 5-a] -pyrimidin-5-ol; Bel 2- (3-amino pyrazolo- [1,5-a] -pyrimidine-7-ylamino) -ethanol; B 3-amino-7-β-hydroxyethylamino-5-methyl-pyrazolo- [1,5-a] -pyrimidine; Bel 2- (7-amino pyrazolo- [1, 5-a] -pyrimidin-3-ylamino) -ethanol; B 2- [(3-Amino-pyrazolo- [1, 5-a] -pyrimidin-7-yl) - (2-hydroxyethyl) -amino] -ethanol; B 2- [(7-amino-pyrazolo- [1, 5-a] -pyrimidin-3-yl) - (2-hydroxyethyl) -amino] -ethanol; as well as its addition salts and tautomeric forms when there is a tautomeric equilibrium. The pyrazolo- [1, 5] -pyrimidine derivatives of the formula (I) as well as their addition salts and their tautomeric forms as defined above can also be used as the oxidation base in and for the preparation of compositions intended for photography or Chemical Engineering. The following examples are intended to illustrate the invention without thereby limiting the scope.

EXAMPLE 1: PIRAZOLO- [1, 5-a] -PIRIMIDINE-3,7-DIAMINE DICHLORHYDRATE Ia STAGE: 3-NITRO-PIRAZOLO- [1, 5-a] -PIRIMIDIN-7-DIAMINE DICHLORHYDRATE 50 grams of 4-nitro-2H-pyrazol-3-ylamine hydrochloride (prepared according to H. Dorn and H.) are introduced into a three-neck flask of 500 cm.sup.3 provided with a mechanical stirring and equipped with a refrigerant and a thermometer.

Dilcher, Liebigs Ann. Chem., 141, 1967), 35 g of β-ethoxy acrylonitrile and 250 cm 3 of acetic acid. The medium is refluxed for 4 and a half hours. Allow to cool to 40 C, then filter the precipitate. The mixture is recovered under stirring in 300 cm.sup.3 of ethyl ether. The precipitate is again filtered, washed on the filter with 100 cm.sup.3 of ethyl ether and dried under vacuum and on phosphoric anhydride. 61.3 of 3-nitro-pyrazolo [1, 5-a] -pyrimidin-7-ylamine hydrochloride are obtained in the form of a yellow powder. (Performance = 93%) NMR (DMSO d6): 6.70 (d; 1H); 8.34 (d; 1H); 8.99 (s; 1H); 9.56 (s; NH2); 11.96 (s; NH +) ELEMENTAL ANALYSIS: C- H5 N- O.,. HCl PM = 215.6 2nd STAGE: PIRAZOLO- [1, 5-a] -PIRIMIDIN- 3,7-DIAMINE DICHLORHYDRATE grams of 3-nitro-pyrazolo- [1,5-a] -pyrimidin-7-ylamine hydrochloride are introduced into a 1000 cm3 three-necked flask fitted with a magnetic stirrer and equipped with a coolant and a thermometer. 7 grams of palladium on carbon at 10%, 85 grams of cyclohexene and 600 cm3 of acetic acid. The medium is refluxed for 4 and a half hours, then the catalyst is filtered on celite. This impregnated catalyst is recovered at reflux with 500 cm.sup.3 of water and filtered again. The two filtrates come together and evaporate. 40 g of beige powder are obtained. This solid is recovered in 55 cm3 of concentrated hydrochloric acid and refluxed for 3 hours. The product was filtered at 15 C and dried under vacuum and over phosphoric anhydride. 25 g of ground white powder are obtained and recrystallized from 80 cm 3 of concentrated hydrochloric acid. 18 g of pyrazolo- [1,5-a] -pyrimidine-3,7-diamine dihydrochloride was collected as a white powder. (Yield = 60%).

NMR (DMSO d): 6.45 (d; 1H); 8.36 (d; lH); 8.39 (s; 1H); 8.60-11.50 (6H) ELEMENTAL ANALYSIS: C, H, N ,. 2HC1.0,5H? OR EM = 231 EXAMPLE 2: 3-AMINO-PIRAZOLO- [1, 5-a] PYRIMIDIN-7-OL CHLORHYDRATE Ia STAGE: 3-NITRO-PIRAZOLO- [1, 5-a] -PIRIMIDIN-7-OL They are introduced into a three-necked flask of 50 cm3 provided with a magnetic stirring and equipped with a refrigerant and a thermometer, 2 g of 4-nitro-2H-pyrazol-3-ylamine hydrochloride (prepared according to H. Dorn and H. Dilcher, Liebigs Ann. Chem., 707, 141, 1967), 1.55 g of methyl 3-methoxy acrylate and 20 cm 3 of absolute ethanol. The medium is refluxed for 5 hours, then the precipitate is filtered hot. 1.2 g of the yellow solid are obtained. After chromatography on silica gel (MERCK: 230-400 mesh, AcOET / MeOH = 9 / l), 0.4 g of 3-nitro-pyrazolo- [1,5-a] -pyrimidin-7-ol was collected. in the form of yellow powder. (Yield = 18%).

NMR (DMSO d6): 6.19 (d; 1H); 7.98 (d; 1H); 8.75 (s; 1H); 13.10 (OH) 2nd STAGE: 3-AMINO-PIRAZOLO- [1, 5-a] -PIRIMIN-7-0L CHLORHYDRATE A 0.25 g 3-nitro-pyrazolo-n, 5-a] -pyrimidin-7-ol is added to a 50 cm3 three-necked flask equipped with a magnetic stirrer and equipped with a coolant and a thermometer. cm3 of acetic acid, 1.6 g of cyclohexene and 85 mg of palladium 10%. The medium is refluxed for 1.5 hours, then the catalyst is filtered on celite. After evaporation of the acetic acid, the solid obtained at reflux of 2 cm 3 of the concentrated hydrochloric acid is recovered for 2 and a half hours. After evaporation of the solvent, a crushed white solid is collected.

NMR (D20): 5.93 (d; 1H); 7.87 (d; lH); 8.04 (s; 1H) EXAMPLE 3: CHLORHYDRATE OF 3-AMINO-5-METHYL-PIRAZOLO- [1, 5-a] -PIRIMIDIN-7-OL I a STAGE: 3-NITRO-5-MET IL-PIRAZOLO- [1, 5-a] - PIRIMIDIN-7-0L 500 g of 3-necked flask equipped with magnetic stirring, a thermometer and a coolant, 50 g of 4-nitro-2H-pyrazole-3-ylamine hydrochloride (prepared according to H. Dorn and H. Dilcher , Liegigs Ann. Chem., 707, 141, 1967) and 60 g of acetoacetate in 160 cm3 of acetic acid. The reaction medium is refluxed for 12 hours. The precipitate that has formed is filtered at 90 ° C. It is rinsed with diisopropyl ether and dried in vacuo over phosphoric anhydride. 50 g of 3-nitro-5-methyl-pyrazolo [1, 5-a] -pyrimidin-7-ol are obtained in the form of yellow crystals (yield = 84.5%, p.f = 290C with decomposition). 0 NMR (DMSOdd): 2.42 (s, 3H); 6.03 (s, 1H); 8.61 (d, 1H); 12, 69 (S, 1H) ELEMENTAL ANALYSIS: C- H- N4 03 PM = 194, 15 H N Calculated (%) 43.31 3.12 28.86 24.72 Found (%) 43.22 3.11 28.77 24.65 2nd STAGE: CHLORHYDRATE OF 3-AMIN0-5-METHYL-PIRAZ0L0- [1, 5-a] -PIRIMIDIN-7-OL In a 1 liter autoclave, 150 cm 3 of acetic acid and 150 cm 3 of water are introduced, then 10 g of 3-nitro-5-methyl-pyrazolo- [1,5-a] -pyrimidin-7-ol and 1 g of palladium on charcoal at 5% containing 50% moisture (ENGELHARD). 5 bars of hydrogen are introduced into the reactor, preheated to 30 ° C. After one hour of reaction the catalyst is filtered on celite. The filtrate is acidified with 100 cm3 of a 7M hydrochloric acid solution. The hydrochloride is precipitated with stirring. It is filtered and washed with diisopropyl ether. 4.2 g of 3-amino-5-methyl-pyrazolo [1, 5-a] -pyrimidin-7-ol hydrochloride are obtained in the form of white crystals. (Yield = 41%).

NMR (DMSO dd): 2.37 (s, 3H); 5.71 (s, 1H); 8.00 (s, 1H); 10.32 (s broad 3H); 13.09 (s wide 1H) ELEMENTAL ANALYSIS: C- H8 N- O. HCl PM = 200.63 EXAMPLE 4: DICHLORHYDRATE OF 3-AMINO-7-β-HYDROXYETHYL-AMINO-5-METHYL-PIRAZOLO- [1,5-a] -PIRIMIDINE Ia STEP: 7-CHLORINE-5-METHYL-3-NITRO-PIRAZOLO- [1, 5-a] - PI RIMIDINE NO, 230 cm3 of phosphorus oxychloride, 15.4 g of N, are introduced into a 500 cm3 three-necked flask equipped with magnetic stirring, a thermometer and a refrigerant., N-dimethyl aniline and 23.3 g of 3-amino-5-methyl-pyrazolo- [1, 5-a] -pyrimidin-7-ol. The reaction medium is refluxed for 2.5 hours. After the phosphorus oxychloride is evaporated under reduced pressure, a very viscous green oil is obtained, to which approximately 400 g of ice was added. A brown solid precipitates. After 30 minutes of stirring, it is filtered and rinsed with petroleum ether, then with diisopropyl ether. After drying under vacuum over phosphoric anhydride, 21.4 g of 7-chloro-5-methyl-3-nitro-pyrazolo- [1,5-a] -pyrimidine are obtained as a tan solid (yield = 83.9%).

NMR (DMSO d6): 2.70 (s, 3H); 7.82 (s, 1H); 9.10 (s, 1H) 2nd STAGE: 7-ß-HYDROXYETHYLAMINE-5-METHYL-3-NITRO-PIRAZOLO- [1,5-A] -PIRIMIDINE H In a 250 cm3 three-necked flask equipped with magnetic stirring, a thermometer and a refrigerant, 15 g of 7-chloro-5-methyl-3-nitro-pyrazolo- [1,5-a] -pyrimidine are introduced into the flask. 100 cm3 of ethanol. 5 g of ethanolamine are added dropwise and the medium is refluxed for 30 minutes. After cooling to room temperature, the yellow precipitate is filtered. Rinse with diisopropyl ether. After drying under vacuum and over phosphoric anhydride, 14.2 g of 7-β-hydroxyethylamino-5-metal-3-nitro-pyrazolo- [1,5-a] -pyrimidine in the form of yellow crystals, (yield = 86%, p.f. = 231 ° C).

NMR (DMSO dd): 2.52 (s, 3H); 3.52 (ra, 2H); 3.66 (, 2H); 4.96 (t, 1H); 6.64 (s, 1H); 8.48 (t, 1H); 8.89 (s, 1H) ELEMENTAL ANALYSIS C, H "N5 O, MW = 237.22 3rd STAGE: DICHLORHYDRATE OF 3-AMINO-7-ß-HYDROXYETHYL-AMINO-5-METHYL-PIRAZOLO- [1, 5-A] -PIRIMIDINE In a 500 cm3 autoclave, 14 g of 7-β-hydroxyethylamino-5-methyl-3-nitro-pyrazolo- [1,5-a] -pyrimidine in 150 cm3 of acetic acid and 150 cm3 of water are introduced, then 1 g of 5% palladium on carbon containing 50% moisture (ENGELHARD). The reaction medium is pre-heated to 30 C and 8 bar of hydrogen pressure are introduced. The reaction starts immediately and the temperature reaches 60C. At the end of the reaction, the catalyst is filtered on celite. The filtrate is acidified with a 7M hydrochloric acid solution. The hydrochloride is precipitated with stirring. It is filtered and washed with diisopropyl ether. 10 g of 3-amino-7-β-hydroxyethylamino-5-methyl-pyrazolo- [1, 5-a] -pyrimidine dihydrochloride in the form of slightly gray crystals. (Yield = 60%).

NMR (D-O): 2.73 (s, 3H); 3.91 (m, 2H); 3.98 (m, 2H); 6.66 (s, 1H); 8.39 (s, 1H) ELEMENTAL ANALYSIS: C- H13 Ns 0.2 HCl MW = 280,16 EXAMPLE 5: 2-METHYL-PIRAZOLO- [1, 5-a] PYRIMIDIN-3, 7-DIAMINE DICHLORHYDRATE Ia STAGE: 2-METHYL-PIRAZ0L0- [1, 5-a] PYRIMIDIN-7-ILAMINE CHLORHYDRATE In a 500-cm3 three-necked flask equipped with magnetic stirring, a thermometer, and a refrigerant, 150 cm3 of 35% hydrochloric acid are introduced and 47.5 of 3-amino-5-methylpyrazole are added dropwise to the flask. a solution of 100 cm3 of water. The temperature is maintained at 60C. Then 47.5 g of 3-ethoxyacrylonitrile are added and the reaction is brought to reflux for 1 hour. The reaction medium is cooled and concentrated under reduced pressure. 50 cm 3 of acetone is added again and the precipitate obtained is filtered. It is washed with diisopropyl ether. After drying under vacuum over phosphoric anhydride, 78.7 g of 2-methyl-pyrazolo- [1, 5-a] -pyrimidin-7-ylamine hydrochloride are obtained in the form of white crystals (yield = 83%).

NMR (DMSO d6): 2.43 (s, 3H); 6.42 (s, 1H); 6.46 (d, 1H); 8.26 (d, 1H); 9.55 (broad s, 1H); 10.32 (s, width 1H) ELEMENTAL ANALYSIS: C- H8 ^ .HCl.0.5 H-O PM = 193.63 2nd STAGE: 2-METHYL-3-NITRO-PIRAZOLO- [1, 5-a] -PIRIMIDIN-7-ILAMINE In a 100 cm three-necked flask equipped with magnetic stirring, a thermometer and a refrigerant, 27 cm3 of 98% sulfuric acid are introduced, then 5.5 g of 2-methyl-pyrazolohydrochloride [1] is dissolved. 5-a] -pyrimidin-7-ylamine in small portions at 5C. Then a mixture of 1.98 g of fuming nitric acid and 5 cm 3 of 98% sulfuric acid is added dropwise over 30 minutes. After 2 hours and a half of reaction, the medium is poured into 200 cm 3 of ice water and neutralized with 122 g of 20% ammonia. The precipitate that forms is filtered. After drying under vacuum over phosphoric anhydride, 3.8 g of 2-methyl-3-nitro-pyrazolo- [1, 5-a] -pyrimidin-7-ylamine is obtained in the form of a green powder (Crude yield = 66 %).

NMR (DMSO d6): 2.62 (s, 3H); 6.39 (d, 1H); 8.39 (broad s, 2H) 3rd STAGE: DICHLORHYDRATE OF 2-METHYL-PIROZOLO- [1, 5-a] -PIRIMIDIN-3, 7-DIAMINE In a 250 cm3 reactor, 3.9 g of 2-methyl-3-nitro-pyrazolo- [1,5-a] -pyrimidin-7-ylamine are introduced into 150 cm3 of methanol then 0.42 g of palladium on 5% carbon containing 50% moisture (ENGELHARD). 10 bar of hydrogen pressure is introduced into the reactor and brought to the medium at 90 ° C. After 40 minutes of reaction, the catalyst is filtered over celite and a stream of gaseous hydrochloric acid is passed through the filtrate. After one hour of stirring, the precipitate is filtered. It is washed with diisopropyl ether and dried under vacuum over phosphoric anhydride. 2.2 g of 2-methyl-pyrazolo- [1,5-a] -pyrimidin-3,7-diamine dihydrochloride are obtained in the form of gray crystals (yield = 46.5%).

NMR (DMSO d6): 2.60 (s, 3H); 6.50 (d, 1H); 8 45 (d, 1H); 9.98 (broad s, 2H); 10.88 (broad s, 4H) ELEMENTAL ANALYSIS: C- H- N-.2HC1 PM = 236.1 EXAMPLES OF APPLICATION EXAMPLES FROM 1 TO 9 OF TINT IN ALKALINE The following dye compositions according to the invention were prepared: (contents in grams): (*) dye support 1 common: B ethanol at 96 ° 9.0 g B salt pentasodic diethylene triaminopentaacetic acid 0.54 g B 35% sodium metabisulfite 0.29 g B 20% ammonia 5.0 g B demineralized water csp 50 g At the time of use, each of the dyeing compositions 1 to 9 was mixed with an amount of 50 g of a 20 volume hydrogen peroxide solution (6% by weight), the pH of which was adjusted to approximately 2.5. with orthophosphoric acid. Each resulting composition is applied immediately for 30 minutes on wicks of natural gray hair with 90% white or permanent, at the rate of g per 1 g of hair. The hair strands were then rinsed, washed with a normal shampoo, then dried. The wicks of hair were dyed in the shades shown in the following table: EXAMPLES OF 10 TO 18 TINT IN ACID MEDIUM and prepared the following dyeing compositions, according to the invention, (contained in grams): • t- cn (**) common dye 2 support: -96 ° 9 '° 9 ethanol-pentasodic diethylene triamino-acetic acid-free °' 54 9 B 35% sodium metabisulfite 0.29 g B K2HP04 / KH2P04 (1.5M / 0.5M) 5, O g B deminetalized water csp 50 g At the time of use, each of the dyeing compositions 10 to 18 is mixed with an amount of 50 g of a 20 volume hydrogen peroxide solution (6% by weight), the pH of which is adjusted to approximately 2.5 with orthophosphoric acid. Each resulting composition is applied immediately for 30 minutes on wicks of natural gray hair with 90% white or permanent, at a rate of 10 g per 1 g of hair. The hair strands were then rinsed, washed with a normal shampoo, then dried.

The wicks of hair were dyed in the shades shown in the following table: EXAMPLES FROM 19 TO 21 OF TINT IN ALKALINE MEDIUM The following dyeing compositions were prepared according to the invention (contained in grams): (*) dye support 1 common: It is identical to the one used in the previous examples 1 to 9.

The dyes were then carried out according to the procedure described above for the above examples 1 to 9. The wicks of hair were dyed in the shades shown in the following table: EXAMPLES 22 TO 24 OF DYE IN ACID MEDIUM The following dyeing compositions were prepared, according to the invention,. { contents in grams): A * common dye 2 support: It is identical to that used in the previous 10 to l examples The dyes were made according to the procedure described above for examples 10 to 18 above. The wicks of hair were dyed in the shades shown in the following table: COMPARATIVE EXAMPLES 25 TO 32 The following dyeing compositions were prepared according to the invention (contained in grams): G? lo? n or cp I heard (*) dye support 1 common: It is identical to the one used in the previous examples 1 to 9. (***): Examples that do not form part of the invention. The dyes were then made on wicks of natural gray hair with 90% white, according to the procedure described above for examples 1 to 9 above. The color of the wicks is then evaluated in the MUNSELL system by means of a CM 2002 MINOLTA colorimeter.

The wicks of hair thus dyed were then subjected to a shampoo resistance test (automatic machine). To do this, the hair strands were placed in a container that has been immersed in a normal shampoo solution at 37C. The basket underwent a variable vavén movement of variable frequency as well as a rotation movement that reproduces the action of a manual rubbing, which produces the formation of foam. After 3 minutes of testing, the strands that were rinsed were removed, then dried. The dyed wicks were subjected to 6 consecutive shampooing tests. The color of the wicks is evaluated again in the MUNSELL system by means of a CM 2002 MINOLTA colorimeter in order to determine the degradation of the colorations after these 6 washes with shampoos. According to the MUNSELL notation, a color is defined by the expression HV / C, in which the three parameters designate respectively the tint or hue (H), the intensity or value (V) and the purity or chromaticity O, the oblique bar of this expression is simply a convention and does not indicate a relationship. The color difference between two wicks is calculated by applying the NICKERSON formula:? E = 0.4 Co? H + 6? V + 3? C, as described for example in "Coleur, Industrie et Technique "; pages 14-17, volume No. 5; 1978. In this formula,? E represents the color difference between two wicks,? H,? V and? C represents the variation in absolute value of the parameters H, V, and C and Co represents the purity of the wick in relation to which it is desired to evaluate the color difference.

The results are given in the following table: (***) the examples that are not part of the invention.

These results show that the compositions of Examples 25, 27, 29 and 31 according to the invention, ie containing pyrazolo [1,5-a] -pyrimidine-3,7-diamine dihydrochloride as an oxidation base , lead to a coloration that resists shampoos better than the compositions of examples 26, 28, 30 and 32 that do not form part of the invention, that is, they contain 4,5,6,7-tetrahydro pyrazolohydrochloride [1,5-a] -pyrimidine-3-ylamine as oxidation base, as described for example in the German patent application D? 4 133 957.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property.

CLAIMS 1. A composition for oxidation dyeing of keratin fibers and in particular human keratin fibers such as hair, characterized in that it comprises, in a medium suitable for dyeing, at least one pyrazolo derivative [1,5 -a] -pyrimidine of the formula (I) given below as oxidation base and / or one of its addition salts with an acid or a base and / or one of its tautomeric forms, when there is a tautomeric equilibrium: wherein: Ri, R2, R3, and R4 designate, identical or different, a hydrogen atom, an alkyl radical of C? -C, an aryl radical, a hydroxyalkyl radical of Cx-C, a

Claims (19)

1. ES! C -C -C polyhydroxyalkyl radical, a (C ~ C) alkoxy C 1 -C 4 alkyl radical, an amino C 1 -C 4 alkyl radical (the amine may be protected by an acetyl, a ureide, a sulfonyl ), a radical (C? -C4) alkyl amino C? -C alkyl, a di- [(C? -C4) alkyl] amino C? -C alkyl radical (the dialkyls can form an aliphatic or heterocyclic 5 or 6 links), a hydroxy radical (C? -C4) alkyl- or di- [hydroxy (Ci-C) alkyl] -amino C? -C4 alkyl; - the radicals X designate, identical or different, a hydrogen atom, an alkyl radical of C? -C4, an aryl radical, a hydroxyalkyl radical of C? -C4, a polyhydroxyalkyl radical of C2-C4, an amino alkyl radical of C? -C, a radical (C? -C4) alkyl amino C1-C4 alkyl, a di- [(C_-C) alkyl] amino alkyl radical of C? -C (the dialkyls can form an aliphatic or heterocyclic cycle of 5 or 6 links), a hydroxy radical (C? -C) alkyl or di- [hydroxy (C 1 -C 4) alkyl] amino C 1 -C 4 alkyl, an amino radical, a radical (C 1 -C 4) alkyl- or di- [(C 1 -C 4) alkyl] -amino; a halogen atom, a carboxylic acid group, a sulfonic acid group; - i equals 0, 1, 2 or 3; - p equals 0 or 1 - q equals 0 or 1 - n equals 0 or 1; with the proviso that: - (i) the sum of p + q is different from 0; (ii) when p + q equals 2, then n equals 0 and the groups NR? R and NR3R4 occupy the positions (2,3); (5,6); (6,7); (3.5); or (3,7); (iii) when p + q equals 1, then n equals 1 and the group NR? R2 (or NR3R4) and the group OH occupy the positions (2,3); (5,6); (6,7); (3.5); or (3,7).
2. 2. A composition according to claim 1, characterized in that the pyrazolo- [1, 5-a] -pyrimidine derivatives of the formula (I) are chosen from: - pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine; - 2-methyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; - 2,5-dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; - pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; - 2,7-dimethylpyrazolo- [1,5-a] -pyrimidine-3,5-diamine; - 3-amino pyrazolo- [1,5-a] -pyrimidin-7-lo; - 3-amino-5-methyl pyrazolo- [1, 5-a] -pyrimidin-71o; - ol 3-amino pyrazolo- [1, 5-a] -pyrimidin-5-lo; 2- (3-amino pyrazolo- [1, 5-a] -pyrimidin-7-ylamino) -ethanol; - 3-amino-7-β-hydroxyethylamino-5-methyl-pyrazolo- [1,5-a] -pyrimidine; 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino) -ethanol; Gl 2- [(3-Amino-pyrazolo- [1, 5-a] -pyrimidin-7-yl) - (2-hydroxy-thiyl) -amino] -ethanol; - Cl 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-dimethylpyrazolo- [1,5-a] -? irimidine-3,7-diamine; 2,5, N-7, N-7-tetramethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; and its addition salts and tautomeric forms, when there is a tautomeric equilibrium.
3. 3. A composition according to any of the preceding claims, characterized in that the one or more pyrazolo- [1,5-a] -pyrimidine derivatives of the formula (I) represent from 0.0005 to 12% by weight of the total weight of the dye composition.
4. 4. A composition according to claim 4, characterized in that the pyrazolo- [1, 5-a] -pyrimidine derivative (s) of the formula (I) represent from 0.005 to 6% by weight of the total weight of the dye composition.
5. 5. A composition according to any of the preceding claims, characterized in that the appropriate medium for the dye (or support) is constituted by water or by a mixture of water and by at least one organic solvent selected from the lower alkanols of C1- C4, glycerol, the glycols and ethers of glycols, the aromatic alcohols, the analogous products and their mixtures.
6. 6. A composition according to any of the preceding claims, characterized in that it has a pH comprised between 3 and 12.
7. 7. A composition according to any one of the preceding claims, characterized in that it includes at least one additional oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases other than the derivatives of pyrazolo- [1, 5-a] -pyrimidine of the formula (I) •
8. 8. A composition according to claim 7, characterized in that the additional oxidation base (s) represent from 0.0005 to 12% by weight of the total weight of the dye composition.
9. 9. A composition according to any of the preceding claims, characterized in that it includes at least one copulator and / or at least one direct dye.
10. 10. A composition according to claim 9, characterized in that or the couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers, and their addition salts.
11. 11. A composition according to any of claims 9 to 10, characterized in that the copulators or copulators represent from 0.0001 to 10% by weight of the total weight of the dye composition.
12. 12. A composition according to any of the preceding claims, characterized in that the addition salts with an acid are chosen from the hydrochlorides, the hydrobromides, the sulfates and the tartrates, the lactates and the acetates and because the addition salts with an base are chosen from those obtained with soda, potash, ammonia or amines.
13. 13. A dyeing process for keratin fibers and in particular for human keratin fibers such as hair, characterized in that at least one dye composition is applied to these fibers as defined in any of claims 1-12 during enough time to develop the desired coloration, either in the air, or with the help of an oxidizing agent, possibly in the presence of oxidation catalysts.
14. 14. A method according to claim 13, characterized in that the coloration is revealed at the sole contact of oxygen in the air.
15. 15. A process according to claim 13, characterized in that the color is revealed at acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added at the moment of use to the dyeing composition or which is present in a oxidizing composition applied simultaneously or sequentially separately.
16. 16. A process according to claim 13 or 15, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates.
17. 17. A multi-compartment device, or multi-compartment dye kit, of which a first compartment includes a dye composition as defined in any of claims 1 to 12 and a second compartment includes an oxidizing composition.
18. 18. The pyrazolo- [1, 5-a] -pyrimidine derivatives, their addition salts with an acid or a base and their tautomeric forms when there is a tautomeric equilibrium, having the formula: wherein: Ri, R2, R3, and R denote, identical or different, a hydrogen atom, a C1-C4 alkyl radical, an aryl radical, a hydroxyalkyl radical of C1-C4- a polyhydroxyalkyl radical of C2- C4, a (C1-C4) alkoxy C1-C4 alkyl radical, an amino-C1-C4 alkyl radical (the amine may be protected by an acetyl, a ureide, a sulfonyl), a (C1-C4) alkyl amino radical C.sub.1 -C.sub.4 alkyl, a di- [(C.sub.1 -C.sub.4) alkyl] amino C.sub.1 -C.sub.4 alkyl radical (the dialkyls can form an aliphatic or 5- or 6-membered heterocyclic cycle), a hydroxy radical (C.sub.1 -C.sub.4) alkyl- or di- [hydroxy (C-C4) alkyl] -amino C? -C4 alkyl; - the radicals X designate, identical or different, a hydrogen atom, an alkyl radical of C? -C4, a hydroxyalkyl radical of C1-C4, a polyhydroxyalkyl radical of C2-C4, an amino radical of C1-C4 alkyl, a radical (C 1 -C 4) alkyl amino C 1 -C 4 alkyl, a di- [(C 1 -C 4) alkyl] amino] C 1 -C 4 alkyl radical (the dialkyls can form an aliphatic or heterocyclic cycle of 5 or 6 links), a hydroxy radical (C 1 -C 4) alkyl or di- [hydroxy (C 1 -C 4) alkyl] amino C 1 -C 4 alkyl, an amino radical, a radical (C 1 -C 4) alkyl-A di- [(C 1 -C 4) alkyl] -amino; a halogen atom, a carboxylic acid group, a sulfonic acid group; - i equals 0, 1, 2 or 3; - p equals 0 or 1 - q equals 0 or 1 - n equals 0 or 1; with the proviso that: - (i) the sum of p + q is different from 0; - (ii) when p + q equals 2, then n equals 0 and the groups NR? R2 and NR3R4 occupy the positions (2,3); (5,6); (6,7); (3.5); or (3,7); - (iii) when p + q equals 1, then n equals 1 and the group NRXR2 (or NR3R) and the group OH occupy the positions (2,3); (5,6); (6,7); (3.5); or (3,7); except for the following compounds: I Pyrazolo- [1,5-a] -pyrimidine-6,7-diamine; I 5,6-Dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; i 2,6-Dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; i 2.5, N7, N7-tetramethyl pyrazolo- [1, 5-a] -pyrimidine-3,7-diamine; 1 2,3-Dimethylpyrazolo- [1,5-a] -pyrimidine-6,7-diamine; B 6-amino-5-methyl-pyrazolo- [1, 5-a] -pyrimidin-7-ol; B 2,5-Dimethyl-6-phenyl- [1, 5-a] -pyrimidine-3,7-diamine; B 2,6-Dimethyl-5-benzyl- [1,5-a] -pyrimidine-3,7-diamine; and its addition salts.
19. 19. The derivatives according to claim 18, selected from the group consisting of: B Pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; B 2-Methyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; B 2,5-Dimethylpyrazolo- [1,5-a] -pyrimidine-3,7-diamine; B Pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; B 2,7-Dimethylpyrazolo- [1,5-a] -pyrimidine-3,5-diamine; Bel 3-amino pyrazolo- [1, 5-a] -pyrimidin-7-ol; B 3-amino-5-methyl-pyrazolo- [1, 5-a] -pyrimidin-7-ol; Bel 3-amino pyrazolo- [1, 5-a] -pyrimidin-5-ol; Bel 2- (3-amino pyrazolo- [1,5-a] -pyrimidine-7-ylamino) -ethanol; B 3-amino-7-β-hydroxyethylamino-5-methyl-pyrazolo- [1,5-a] -pyrimidine; Bel 2- (7-amino pyrazolo- [1, 5-a] -pyrimidin-3-ylamino) -ethanol; Bel 2- [(3-amino-? Irazolo- [1, 5-a] -pyrimidin-7-yl) - (2-hydroxyethyl) -amino] -ethanol; B 2- [(7-amino-pyrazolo- [1, 5-a] -pyrimidin-3-yl) - (2-hydroxyethyl) -amino] -ethanol; as well as its addition salts and tautomeric forms when there is a tautomeric equilibrium. SUMMARY OF THE INVENTION The invention relates to novel compositions for the oxidation dyeing of keratin fibers comprising at least one particular pyrazolo- [1,5-a] -pyrimidine derivative, the dyeing process employing this composition, new pyrazolo- [1] derivatives. 5-a] -pyrimidine as well as its preparation procedure.