FR3060002A1 - NOVEL DERIVED OXIDATION BASES OF 5-AMINOPENTYL-4,5-DIAMINOPYRAZOLE, THE COMPOSITION CONTAINING SAME AND THEIR USE IN KERATIN FIBER OXIDATION DYE - Google Patents

Abstract

The present invention relates to novel compounds derived from 5-aminopentyl-1H-pyrazole-4,5-diamine, a composition for the oxidation dyeing of keratinous fibers containing them, a process for the preparation of said 5-aminopentyl derivatives -1H-pyrazole-4,5-diamine, reaction intermediates, an oxidation dyeing process using the composition, the use of said 5-aminopentyl-1H-pyrazole-4,5-diamine derivatives for the oxidation of keratin fibers and a kit. Compounds derived from 5-aminopentyl-4,5-diaminopyrazole of formula (I) below: As well as their addition salts with organic or inorganic acids, their tautomers, their solvates such as hydrates; wherein R, R1, R2, R3 and R4 are as defined in the description.

Description

® FRENCH REPUBLIC

NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number:

(to be used only for reproduction orders)

©) National registration number

060 002

62211

COURBEVOIE © Int Cl ⁸ : C 07 D 231/38 (2017.01), C 07 D 403/06, 207/04, A 61 K 8/49, A 61 Q 5/10

A1 PATENT APPLICATION

©) Date of filing: 09.12.16. (© Applicant (s): L'OREAL Société anonyme— FR. (© Priority: @ Inventor (s): FADLI AZIZ and LIU ZHIBO. ©) Date of public availability of the request: 15.06.18 Bulletin 18/24. ©) List of documents cited in the preliminary search report: See the end of this booklet (© References to other related national documents: ©) Holder (s): L'OREAL Société anonyme. ©) Extension request (s): (© Agent (s): L'OREAL Société anonyme.

NOVEL OXIDATION BASES DERIVED FROM 5-AMINOPENTYL-4,5-DIAMINOPYRAZOLE, THE COMPOSITION CONTAINING THEM AND THEIR USE IN OXIDATION DYES FOR KERATINIC FIBERS.

FR 3 060 002 - A1 (u / d The present invention relates to new compounds derived from 5-aminopentyl-1 H-pyrazole-4,5-diamine, a composition for the oxidation dyeing of keratin fibers containing it (s) , a process for the preparation of said 5-aminopentyl-1 H-pyrazole-4,5-diamine derivatives, reaction intermediates, an oxidation dyeing process using the composition, the use of said 5-aminopentyl-1 H derivatives -pyrazole-4,5-diamine for the oxidation dyeing of keratin fibers as well as a kit.

The compounds derived from 5-aminopentyl-4,5-diaminopyrazole of formula (I) below:

(i)

As well as their addition salts with organic or mineral acids, their tautomers, their solvates such as hydrates; wherein R, R !, R ₂ , R ₃ and R ₄ are as defined in the description.

NEW OXIDATION BASES DERIVED FROM 5 AMINOPENTYL-4,5-DIAMINOPYRAZOLE, THE COMPOSITION

CONTAINER AND THEIR USE IN OXIDATION DYEING OF KERATINIC FIBERS.

The present invention relates to new compounds derived from 5 aminopentyl-1 H-pyrazole-4,5-diamine, a composition for the oxidation dyeing of keratin fibers containing it, a process for the preparation of said 5-aminopentyl-1 derivatives. H-pyrazole-4,5-diamine, reaction intermediates, an oxidation dyeing process using the composition, the use of said 5-aminopentyl-1 derivatives H-pyrazole-4,5diamine for oxidation dyeing keratin fibers as well as a kit.

It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors generally called oxidation bases. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds. These oxidation bases are generally ortho- or para-phenylenediamines, ortho or para-aminophenols, heterocyclic compounds such as pyrazole or pyrazolo pyrimidine derivatives.

We also know that we can vary the shades obtained with these oxidation bases by combining them with color modifiers also called couplers, the latter being chosen in particular from aromatic metadiamines, meta-aminophenols, metadiphenols and certain heterocyclic compounds.

The variety of molecules involved in the oxidation bases and couplers allows obtaining a rich palette of colors.

The so-called permanent coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity, to exhibit good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction).

The dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which can be in fact differently sensitized (that is to say damaged) between its tip and its root. They must also have good chemical stability in the formulations. They must have a good toxicological profile.

In addition, for a certain number of applications, dyes are sought which give chromatic and / or intense shades to the hair.

It is already known, for example, in patent application EP 375 977 to use in oxidation dyeing for dyeing keratin fibers 4,5-diaminopyrazole derivatives. Also known in patent applications EP 873 109, EP 871 426 and EP 692 245 are compositions for oxidation dyeing comprising diaminopyrazole derivatives and couplers of the metaphenylenediamine, metaaminophenol or benzoxazine type.

In addition, a series of patent applications describes the use of 1-hexyl-4,5-diaminopyrazole oxidation base in the oxidation dyeing of hair (WO 2013122989, WO 2013122990, US 20120210519, US 20120210520, US 20120210521, US 20120210522, US 20120210524, US 20120210525, and US 20120210526).

However, these compositions do not make it possible to satisfy all of the above requirements, in particular in terms of rise, chromaticity, tenacity in washing, in the light and / or in sweat, and / or the selectivity of the coloring between the root and tip.

The object of the present invention is to develop new compounds and dye compositions which make it possible to obtain wide gamut colors and which do not have the drawbacks of dyes of the prior art. In particular, the object of the invention is to develop powerful colors, particularly chromatic and brilliant, not very selective and having excellent properties of resistance to the various aggressions that keratin fibers can undergo, in particular with regard to light and / or washing and / or sweating.

To this end, the subject of the present invention is new compounds derived from 5-aminopentyl-1H-pyrazole-4,5-diamine, of formula (I) below:

As well as their addition salts with organic or mineral acids, their tautomers, their solvates such as hydrates;

io Formula (I) in which • R represents an atom or group chosen from:

- hydrogen,

- hydroxy,

- ALK representing a (Ci-C6alkyl, or (C2-Ce) alkenyl group, linear or branched, preferably (Ci-C4) alkyl such as methyl; and

- ALK-O- in which ALK is as defined above, preferably (Ci-C4) alkyl such as methyl;

• Ri and R ₂ , identical or different, represent an atom or group chosen from:

- hydrogen;

- C-i-C6 alkyl optionally substituted by one or more hydroxy radicals, preferably C1-C4 and more preferably C1-C2 such as methyl or hydroxymethyl;

- (Ci-C6) alkyl (thio) carbonyl, preferably (Ci-C2) alkylcarbonyl such as acetyl;

or Ri and R ₂ together with the nitrogen atom to which they are attached form a saturated or unsaturated heterocycle of 5 to 8 members, optionally substituted, or a heteroaryl comprising of 5 to 8 members, optionally substituted, this heterocycle or heteroaryl which may contain one or more additional heteroatoms preferably chosen from the oxygen or nitrogen atom, preferably Ri and R ₂ form together with the nitrogen atom a group chosen from imidazolyl piperidino, pyrrolidino, pipérazino, morpholino optionally substituted with a (C1-C4) alkyl group; and • R ₃ and R ₄ , identical or different, represent an atom or group chosen from:

- hydrogen; and

- (Ci-C6) alkyl (thio) carbonyl, preferably (Ci-C2) alkylcarbonyl such as acetyl.

A subject of the invention is also a composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, characterized in that it contains, in a medium suitable for dyeing, as oxidation base at least one compound of formula (I) as defined above, or one of its addition salts with an acid, its tautomers and solvates such as hydrates.

The subject of the invention is also a process for the oxidation dyeing of keratin fibers using such a composition and the use of the 5-aminopentyl-1 H-pyrazole-4,5-diamine derivatives of formula (I) such as defined above, for the coloring of keratin fibers, in particular human fibers such as the hair.

The subject of the invention is also a process for preparing the aminopentyl-1 / - / - pyrazole-4,5-diamine derivatives of formula (I) as defined below and reaction intermediates 6, 6 ′, 7, 7 ', 7 ”, 7”', 8, and 9 'as defined below in summary diagrams 1 and 2.

As indicated above, the colorings obtained from the oxidation dye composition according to the invention are powerful, not very selective, particularly bright and chromatic. They also have excellent resistance properties with regard to the action of the various external agents (light, bad weather, washing, permanent waving, perspiration, friction), in particular with regard to successive shampoos and the light.

In the context of the present invention, unless otherwise indicated, the following terms are understood:

- "alkyl" means a linear or branched radical containing from 1 to 6 carbon atoms, in particular from 1 to 4 carbon atoms, for example methyl, ethyl, n-propyl, iso-propyl, butyl, n-pentyl, n-hexyl, preferably methyl;

- By “alkenyl”, a radical comprising from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, and containing at least one double bond, preferably between 1 and 2 double bonds, conjugated or not, such as ethylenyl;

- By "organic or mineral acid salt" is meant the cosmetically acceptable salts, more particularly the salts derived from i) mineral acids and halogenated acids such as the hydrochloric acid HCl salts, hydrobromic acid HBr , sulfuric acid H2SO4, ii) (Ci-C6) alkylsulfonic acids: Alk-S (O) 2OH such as methylsulfonic acid and ethylsulfonic acid; iii) arylsulfonic acids: Ar-S (O) 2OH with Ar representing an aryl group in particular phenyl such as the salts derived from benzene sulfonic acid and toluene sulfonic acid; iv) (poly) (hydroxy) (C-iC6) alkylcarboxylic acids such as citric acid salts; succinic acid; tartaric acid; lactic acid, x) (C-iC6) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; iv) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; vi) phosphorus acids such as phosphoric acid H3PO4; v) (Ci-C6) alkylcarboxylic acid such as acetic CH ₃ C (O) OH; xiv) triflic acid CF3SO3H and vii) tetrafluoroboric acid HBF ₄ ;

- By "anionic counterion" means an anion or an anionic group derived from organic or mineral acid salt counterbalancing the cationic charge of the compound; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including Ci-C6 alkyl sulfonates: Alk-S (O) 2O 'such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S (O) 2O 'such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkylsulfates: Alk-OS (O) O 'such as methysulfate and ethylsulfate; x) arylsulfates: ArO-S (O) O 'such as benzenesulfate and toluenesulfate; xi) alkoxysulfates: Alk-OS (O) 2O 'such as methoxy sulfate and ethoxysulfate; xii) aryloxysulfates: Ar-OS (O) 2O ', xiii) phosphates O = P (OH) ₂ -O; O = P (O) ₂ -OH O = P (O) ₃ , HO- [P (O) (O)] _W P (O) (O ') 2 with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, xvii) disulfate disulfate (0 =) ₂ S (O) ₂ or SO4 ² 'and monosulfate HSO4';

- the anionic counter ion, derived from organic or mineral acid salt, ensures the electroneutrality of the molecule so it is understood that when the anion comprises several anionic charges then the same anion can be used for the electroneutrality of several cationic groups in the same molecule or can be used for the electroneutrality of several molecules; for example a compound which contains two cationic charges can contain either two anionic counter ions "monoloaded" or either contains an anionic counterion "bicharged" such as (O =) ₂ S (O ') ₂ or O = P (O) ₂ -OH ;

- an “aryl” radical represents a mono or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; particularly the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl, preferably phenyl;

a “heteroaryl radical” represents a mono or polycyclic group, condensed or not, comprising from 5 to 22 links, from 1 to 6 heteroatoms chosen from the nitrogen, oxygen and sulfur atoms, and of which at at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyle, pyridyle, pyridinoimidazolyle, pyrrolyle, quinolyle, tétrazolyle, thiadiazolyle, thiazolyle, thiazolopyridinyle, thiazoylimidazolyle, thiopyryyl;

a “saturated or unsaturated 5 to 8-membered heterocycle” represents a mono or polycyclic group, condensed or not, saturated or containing one or more ethylenic unsaturations, comprising from 5 to 8 members, comprising in at least one ring an N heteroatom, can contain from 1 to 3 additional nonadjacent heteroatoms chosen from the nitrogen, oxygen and sulfur atom, this heterocycle can be substituted by one or more radicals, identical or different chosen from alkyl, hydroxyalkyl, alkoxy radicals preferentially, according to the present invention, the saturated or unsaturated heterocycle of 5 to 8 members, preferably saturated, is chosen from piperidyl, pyrrolidinyl, piperazinyl, morpholinyl;

- the “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radical can be substituted by at least one substituent carried by a carbon atom, chosen from:

a C1-C6 alkyl radical, optionally substituted by one or more radicals chosen from hydroxyl, C1-C2 alkoxy, (poly) hydroxy-C2-C2, acylamino, amino radicals substituted by two identical or different alkyl radicals, in C1-C4, optionally carrying at least one hydroxyl group or, the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, preferably from 5 to 6 members, saturated or unsaturated optionally substituted optionally comprising another heteroatom identical or different from nitrogen;

a halogen atom;

a hydroxyl group;

a C1-C2 alkoxy radical;

a C2-C4 (poly) hydroxyalkoxy radical;

an amino radical;

a 5- or 6-membered heterocycloalkyl radical;

a 5 or 6-membered heteroaryl radical optionally substituted by a (C1-C4) alkyl radical, preferably methyl;

an amino radical substituted by one or two identical or different Ci-C6 alkyl radicals optionally bearing at least:

i) a hydroxyl group, ii) an amino group optionally substituted by one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 chain links, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen;

an acylamino radical (-NR-C (O) -R ') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R' is a C1-C2 alkyl radical;

a carbamoyl radical ((R) ₂ NC (O) -) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group;

an alkylsulfonylamino radical (R'-S (O) 2-N (R) -) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical, a phenyl radical; an aminosulfonyl radical ((R) ₂ NS (O) 2-) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxyl group;

a carboxylic radical in acid or salified form (preferably with an alkali metal or ammonium, substituted or not);

a cyano group;

a nitro or nitroso group;

a polyhaloalkyl group, preferably trifluoromethyl;

The expression "at least one" is equivalent to the expression "one or more".

The keratin fibers treated by the process or that which are used according to the invention are in particular human keratin fibers and preferably the hair.

According to a particular embodiment of the invention, ALK represents a (C-i-C4) alkyl group such as methyl, ethyl, n-propyl, tertrabutyl. Preferably, the compound or compounds of the invention are such that ALK represents a methyl group.

According to a particular embodiment of the invention, the compounds of formula (I) are such that R represents an atom or group chosen from:

Hydrogen;

ALK representing a (C-i-C4) alkyl group; and ALK-O- in which ALK is as defined above;

particularly R represents a hydrogen atom or a (C-iC4) alkyl group, preferably R represents a hydrogen atom.

According to an advantageous embodiment of the invention, the compounds of formula (I) are such that Ri and R ₂ , identical or different, represent an atom or group chosen from:

- hydrogen;

- C1-C4 alkyl optionally substituted by one or more hydroxy radicals, preferably C1-C2 such as methyl or hydroxymethyl; and

- (C-i-C4) alkylcarbonyl, preferably (C-i-C2) alkylcarbonyl such as acetyl.

According to a preferred embodiment of the invention, the compounds of formula (I) are such that R ₃ and R ₄ represent a hydrogen atom.

According to another particular embodiment of the invention, the compounds of formula (I) are such that Ri and R ₂ form, together with the nitrogen atom to which they are attached, a saturated heterocycle of 5 to 7 members, optionally substituted , this heterocycle possibly containing one or two additional heteroatoms chosen from the oxygen or nitrogen atom; preferably chosen from piperidino, pyrrolidino, pipérazino, morpholino optionally substituted by a (Ci-C4) alkyl group such as methyl.

According to another particular embodiment of the invention, the compounds of formula (I) are such that Ri and R ₂ form together with the nitrogen atom to which they are attached a heteroaryl comprising from 5 to 7 members, optionally substituted , this heteroaryl possibly containing one or two additional heteroatoms chosen from the oxygen or nitrogen atom, preferably R 1 and R ₂ form together with the nitrogen atom a group chosen from imidazolyl.

According to a particular embodiment of the invention, the compounds of formula (I) are salified with n organic or mineral acids n HAn, with n =%; 1; 2; 3 or 4; preferably, the acid or acids are chosen from sulphonic acids such as methane sulphonic acid, paratoluene sulphonic acid, sulfuric acid, halogenated acids such as hydrochloric and hydrobromic acid, acids ( poly) (hydroxy) (C-iC6) alkylcarboxylic acids such as acetic acid, citric acid, or tartaric acid; more preferably, An represents a hemi-sulphate, sulphate, hydrochloride, acetate, methanesulphonate group; even more preferably hemisulfate, sulfate and hydrochloride; in particular, n HAn represents 0.5 H ₂ SO ₄ , 1 H ₂ SO ₄ , 2 H ₂ SO ₄ , 2 HCl, 3 HCl, or 4 HCl.

According to a particular embodiment of the invention, the compounds of formula (I) are chosen from the compounds of formula (I ’) below:

ι

R ₂ η

HAn (! ’)

As well as their tautomers and their solvates such as hydrates; formula (I ’) in which:

- R, Ri and R ₂ being as defined above;

- HAn represents an organic or mineral acid with An representing the anionic counter ion of said organic or mineral acid; preferably n HAn is as defined above; and

- n represents an integer or not, inclusive between 0.5 and 4, particularly n is 0.5; 1 or 2 ;

it being understood that when n is greater than or equal to 2 then An can be identical or different between them.

According to a particular embodiment of the invention, the compounds of formula (I) or (I ’) are chosen from those of formula (I”) as well as their solvates such as hydrates:

formula (I ”) in which:

- n represents an integer or not inclusive inclusive between 0.5 and 2, in particular n is 0.5, 1 or 2;

- HAn is as defined above, particularly An is an anionic counter ion chosen from sulfate, hydrochloride, tartrate, acetate, hydrobromide, tosylate, mesylate, methanesulfonate, citrate, more particularly, An is chosen from sulfate, hydrochloride, acetate, and methanesulfonate , preferably An is chosen from sulfate, hydrochloride, and methanesulfonate, more preferably chosen from sulfate, and hydrochloride.

In particular, the compounds of the invention of formula (I), (I ') or (I ”) are such that n HAn represents 0.5 H2SO4, 1 H2SO4 ,, 2 H ₂ SO4, 2 HCl,

3HCI, or 4 HCl.

Preferably, the compounds of the invention of formula (I), (I ’) or (I”) are such that n HAn represents 0.5 H2SO4, 1 H2SO4, 2 HCl.

More preferably, the compounds of the invention of formula (I), (I ') or (I ”) are chosen from the compounds of formula 1 to 32 below as well as their addition salts with organic or mineral acids, their tautomers, their solvates such as hydrates or solvates of linear or branched alcohol such as ethanol or isopropanol:

: 1 - [5- (dimethylamino) pentyl] -1 Hpyrazole-4,5-diamine: 1- [5- (dimethylamino) pentyl] -3methyl-1 / - / - pyrazole-4,5-diamine

: 1 - [5- (diethylamino) pentyl] -1 Hpyrazole-4,5-diamine

OH: 2,2 '- {[5- (4,5-diamino-1Hpyrazol-1-yl) pentyl] imino} diethanol

OH: 1- [5- (diethylamino) pentyl] -3-methyl1 / - / - pyrazole-4,5-diamine: 2,2 '- {[5- (4,5-diamino-3methyl-1 H-pyrazol -1 yl) pentyl] imino} -diethanol

/ Ο ΝΗ, ^Νχ Ν ^ ^ΝΗ 2 / Ο ΝΗ,% ^ νη ₂ λ / Η 11: 1- (5-aminopentyl) -3-methoxy-1 / - / pyrazole-4,5-diamine 12: A / - [5- (4,5-diamino-3-methoxy1 / - / - pyrazol-1 -yl) pentyl] acetamide / Ο ΝΗ,% ^ ΝΗ ₂ / Ο ΝΗ,% ^ ΝΗ ₂ 13: 1- [5- (dimethylamino) pentyl] -3methoxy-1 / - / - pyrazole-4,5-diamine 14: 1 - [5- (diethylamino) pentyl] -3methoxy-1 / - / - pyrazole-4,5-diamine / Ο ΝΗ,% ^ νη ₂ νη ₂ ^Ν ζ ^ ΝΗ ₂ hcl J J Ο I ΟΗ 15: 2.2 '- {[5- (4,5-diamino-3-methoxy-1 / - / pyrazol-1 -yl) pentyl] imino} -diethanol 16: 1- [5- (pyrrolidin-1-yl) pentyl] 1 H-pyrazole-4,5-diamine

: 1 - [5- (morpholin-4-yl) pentyl] -1 Hpyrazole-4,5-diamine: 1 - [5- (piperazin-1 -yl) pentyl] 1 / - / - pyrazole-4,5- diamine

: 1 - [5- (piperidin-1 -yl) pentyl] -1 Hpyrazole-4,5-diamine: 3-methyl-1 - [5- (pyrrolidin-1 yl) pentyl] -1 / - / - pyrazole- 4,5-diamine

: 3-methyl-1- [5- (morpholin-4- 22: 3-methyl-1- [5- (piperazin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine yl) pentyl] -1 / - / - pyrazole-4,5-diamine

1 / - / - pyrazole-4,5-diamine methylpiperazin-1 -y l) penty l] -1 Hpyrazole-4,5-diamine / o nh ₂ ^ nh ₂ / O NH, ⁿ ^ nh ₂ r / 25: 3-methoxy-1- [5- (pyrrolidin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine 26: 3-methoxy-1- [5- (morpholin-4yl) pentyl] -1 / - / - pyrazole-4,5-diamine —0 NH, ^ν 'Λνη ₂ / O NH, ^N ^ NH ₂ H ₃ c ^{/ N} ^ 27: 3-methoxy -1- [5- (4-methylpiperazin1 -y l) penty l] -1 / - / - pyrazole-4,5-diamine 28: 3-methoxy-1- [5- (piperazin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine —O NH, ^N ' _n ^ nh ₂ NH, ^N 'N ^K NH ₂ N ^ 29: 3-methoxy-1- [5- (piperidin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine 30: 1 - [5- (1 / - / - imidazol-1 -yl) pentyl] 1 / - / - pyrazole-4,5-diamine

ⁿ 0nh ₂ / O NH, 0 ^ 0 ^ 31: 1 - [5- (1 / - / - imidazol-1 -yl) pentyl] -3methyl-1 / - / - pyrazole-4,5-diamine 32: 1- [5- (1 / - / - imidazol-1-yl) pentyl] 3-methoxy-1 / - / - pyrazole-4,5diamine

The compound (s) of formula (I), (I ’) and (I”) as defined above are synthesized by conventional methods known to those skilled in the art.

Process for the preparation of the compounds of formula (I) or fl ’) if Ri and R?

represent a hydrogen atom

The compound of structure (I) can be obtained for example via the process of synthesis according to schemes 1 and 2 below having previously synthesized the (thio) aldehydes 4 and 4 ′ from the alcohol or thiol reagents 1 and Γ respectively according to conventional methods known to those skilled in the art (see for example WO 9735836). We can for example cite the methods according to diagrams a) and b) below:

Scheme a) - synthesis of compound 4 from compound 1:

2 3 4 compounds 1 to 4 in which; R _a represents a group (Ci-C6alkyl such as methyl, boc represents a group protecting the amine function, in particular alkylcarbamates such as ter-butylcarbamate; and X represents an oxygen or sulfur atom, preferably oxygen; process for the preparation of compounds 4 consisting in reacting according to the synthetic scheme a) a pentylamine compound 1 comprising a leaving group, preferably hydroxy, and a primary amino group with a (thio) carbonyl compound TC (X) -R _a with X and R _a as defined above and T representing an optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocycloalkyl or optionally substituted cycloalkyl, preferably X represents an oxygen atom and T represents a (hetero) aryl group such as phenyl according to l step i), which after elimination of H ₂ X leads to the imine compound 2 according to step ii); the latter is reduced by conventional reduction method such as with alkali metal hydrides and aluminum or boron or catalytic method under hydrogen such as Ni or Pd on graphite, preferably Ι_ΐΑΙΗ ₄ , to lead to compound 3 with group secondary amino according to step iii); said group -N (H) -CH (R _a ) -T is / V-protected by a conventional method known to those skilled in the art (see for example chap. 7, p. 218 to 287 and 327 of the book “Protective Groups in Organic Synthesis ", TW Greene, 1981) in particular by alkylcarbamates such as terbutylcarbamate, followed by an oxidation step to yield compound 4 according to step iv).

Process for the preparation of the compounds of formula (I) if Ri and R? represent an optionally substituted (Ci-C ₆ ) alkyl group:

Scheme b) - synthesis of compound 4 ’from compound 1’:

1 '

XH

4 '

OH

OH

III

2a

3a

OH

H

4a compounds Γ and 4 'in which X is as defined above ,; R'i and R ' ₂ , identical or different, represent a C1-C6 alkyl group optionally substituted by one or more hydroxy radicals;

process for the preparation of compounds 4 ’consisting in reacting according to the synthetic scheme b) a compound Γ disubstituted pentylamine comprising a leaving group preferably hydroxy followed by an oxidation step to yield compound 4’ according to i).

Scheme 1: synthesis of the compounds of formula (I) for which Ri and R ₂ represent a hydrogen or an alkyl radical (Ci-C6) (thio) carbonyl, preferably io alkyl (Ci-C4) (thio) carbonyl,

x

Compounds 4 to 11 in which R is as defined above in formula (I), T, R _a , boc, X, An and n are as defined above, x is 1 or 2, R _b and R _c , identical or different are as defined for R _a , and Z representing an optionally substituted (hetero) aryl group such as phenyl;

Process which consists in reacting:

- a derivative 4 with a nitrile derivative R-CH = CH-CN with hydrazine to conduct after a nucleophilic reaction of hydrazine on 4 of Michael 1,2 type then addition of the compound R-CH = CH-CN, preferably at low temperature such as 0 ° C and under an inert atmosphere, to yield the compound of formula 5; then

a compound 5 with an alkaline agent, preferably sterically hindered, in particular chosen from alkaline and alkaline earth alkanolates (C3-C-10) of which the alkyl part is branched or sterically hindered, such as alkali metal terbutylates, alkaline earth metal or ammonium preferably sodium or potassium, preferably under an inert atmosphere in an organic solvent preferably polar protic such as (C3-C-io) alkanol whose alkyl part is linear or branched, such as terbutanol for lead after intramolecular cyclization to the 5aminopyrazole 6 derivative;

- Compound 6 which is nitrated or nitrosed in particular in a polar protic solvent such as ethanol and at low temperature such as at 0 ° C. by the addition of (Ci-Cejalkylnitrile, such as isopentyl nitrile, followed by the addition of mineral acid, preferably halogenated such as hydrochloric acid, at low temperature preferably at 0 ° C., then ammonia is added, in particular at a pH above 11, optionally followed by preferably water / halogenomethane extraction such as dichloromethane, optionally followed by filtration to yield the nitro (so) compound 7; or then compound 6 which reacts with a diazonium salt ZN = N ⁺ Q 'with Q' representing a counter anionic ion, and Z representing an optionally substituted aryl or heteroaryl group such as phenyl optionally substituted by a halogen, a (Ci-C4) alkyl group, an SO3R 'group with R' representing a hydrogen atom or an alkali or alkali metal earthy such as sodium; especially in so Like water, an alcohol and at a temperature between -5 ° C and 10 ° C, and once the azo coupling reaction is complete (reaction followed by TLC), to lead to the azo compound 7 'preferably in a medium at neutral pH and precipitates, the solid can be purified by filtration;

if, however, the yield is found to be low due to the solubility of the azo, it can be extracted with a polar aprotic organic solvent of ethyl acetate type or a halogenated solvent, preferably chlorinated, such as dichloromethane and compound 7 ' is isolated after evaporation of the solvent.

compounds 7 or 7 'with a reducing agent such as with a catalyst such as Ni or Pd in the presence of hydrogen or hydrazine preferably under an inert atmosphere in particular in a polar protic solvent such as ethanol to yield the compounds 8, and 9 and 9 belonging to the compound of formula (I) as defined above;

said compound 9 can optionally;

be salified using organic or mineral acid, as defined above, preferably using in particular sulfuric mineral acid such as sulfuric acid to yield compound 11 belonging to the compound of formula (I) as previously defined

- be (thio) acetylated using (thio) ester or (thio) acid R _a -C (X) -X-R ',

Rb-C (X) -X-R ', and R _c -C (X) -XR' with R 'representing a hydrogen atom or a group (Ci-C6alkyl to lead to compound 10 or 12, compound 12 belonging to the compound of formula (I) as defined above.

Scheme 2: synthesis of the compounds of formula (I) for which R 1 and R ₂ represent a group (C 1 -C 6 alkyl optionally substituted by one or more hydroxy groups,

Compounds 4 'to 10' in which R is as defined above in formula (I), T, R _a , boc, X, x, Z, R _a , Rb, R _c , R'i, R'2, An and n are as defined above;

Process which consists in reacting:

- a 4 'derivative with a nitrile derivative R-CH = CH-CN with hydrazine to conduct after a nucleophilic reaction of hydrazine on 4' of Michael 1,2 type then addition of the compound R-CH = CH-CN , preferably at low temperature such as 0 ° C and under an inert atmosphere, to yield the compound of formula 5 '; then

- a 5 ′ compound with an alkaline agent, preferably sterically hindered, in particular chosen from alkaline and alkaline earth alkanolates (C3-Cio) of which the alkyl part is branched or sterically hindered, such as alkali metal terbutylates, alkaline earthy or ammonium, preferably sodium or potassium, preferably under an inert atmosphere in an organic solvent, preferably polar protic such as (C3-Cio) alkanol, the alkyl part of which is linear or branched, such as terbutanol to conduct after cyclization intramolecular to the 5aminopyrazole 6 'derivative;

- compound 6 'which is nitrated or nitrosed in particular in a polar protic solvent such as ethanol and at low temperature such as at 0 ° C by the addition of (Ci-C6) alkylnitrile, such as isopentyl nitrile , followed by the addition of mineral acid, preferably halogenated such as hydrochloric acid, at low temperature preferably at 0 ° C., then ammonia is added, in particular at a pH above 11, optionally followed preferably water / halogenethane extraction such as dichloromethane, possibly followed by filtration to yield the 7 ”nitro (so) compound; or then the compound 6 'which reacts with a diazonium salt ZN = N ⁺ Q' with Q 'and Z as defined above in particular in a solvent such as water, an alcohol and at a temperature between -5 ° C and 10 ° C, and once the azo coupling reaction is complete (reaction followed by TLC), to lead to the 7 ”azo compound preferably in a medium at neutral pH and precipitates, the solid can be purified by filtration; if, however, the yield is found to be low due to the solubility of the azo, it can be extracted with a polar aprotic organic solvent of ethyl acetate type or a halogenated solvent, preferably chlorinated, such as dichloromethane and compound 7 ” 'is isolated after evaporation of the solvent;

compounds 7 ”or 7” with a reducing agent such as with a catalyst such as Ni or Pd in the presence of hydrogen or hydrazine preferably under an inert atmosphere in particular in a polar protic solvent such as ethanol to conduct to the compounds 8 ′ belonging to the compounds of formula (I) as defined above; said compound 8 'can optionally;

be salified using organic or inorganic acid, as defined above, preferably using in particular sulfuric inorganic acid such as sulfuric acid to yield the compound 10 ′ belonging to the compound of formula (I ) as defined above

- be (thio) acetylated using (thio) ester or (thio) acid R _a -C (X) -X-R ', Rb-C (X) -X-R', and R _c - C (X) -XR 'with R' representing a hydrogen atom or a (Ci-C6alkyl) group to yield compound 9 'belonging to the compounds of formula (I) as defined above.

According to a particular embodiment, the compounds (I) are obtained by protection of the primary or secondary amine groups in amide followed by a de-protection of this form followed by salification to isolate the compounds (I). These means of protection and deprotection of primary and secondary amine functions are known to those skilled in the art, for example. ex. chap. 7, p. 249 to 265 of the book “Protective Groups in Organic Synthesis”, T. W. Greene, 1981.

According to a particular embodiment of the invention, the synthesis process uses the synthesis routes via the azo intermediates 7 ’and 7’ ’.

In particular, commercial benzene diazonium salts will be used, chosen from (Ci-C6) (alkyl) benzenediazonium salts such as (Ci-C6) (alkyl) benzenediazonium halide and sulfonate (BENZENEDIAZONIUM

BENZENEDIAZONIUM

BENZENEDIAZONIUM

CHLORIDE-100-34-5, CHLORIDE-2028-34-4,

CHLORIDE-2028-72-0,

2- METHYL3- METHYLPDIAZOBENZENESULFONIC ACID, 305-80-6)

Another subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, characterized in that it contains, in a medium suitable for dyeing, oxidation base titer i) at least one compound of formula (I) as defined above, or one of its addition salts with an acid, its tautomers and solvates such as hydrates.

The composition according to the invention generally contains from 0.001 to 10% by weight, preferably from 0.05 to 6% by weight, and more preferably from 0.1 to 3% by weight, of at least one compound of formula (I) as well as its addition salts with an organic or mineral acid, its tautomers, its solvates such as hydrates.

The composition in accordance with the invention may contain, in addition to i) the compound (s) of formula (I) as defined above, ii) one or more additional oxidation bases (s) ( s) different from the compound (s) of formula (I) which can be chosen from the oxidation bases conventionally used in oxidation dyeing. Particularly the base (s) of additional oxidation (s) is (are) chosen (s) from paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols and heretocyclic bases different from the compound (s) of formula (I) defined above.

According to a particular embodiment, the base (s) of additional oxidation (s) is (are) chosen (s) from para-phenylenediamines and more particularly chosen (s) from para-phenylenediamine, paratoluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethylpara-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, Ν , Νdimethyl-para-phenylenediamine, Ν, Ν-diethyl-para-phenylenediamine, Ν, Ν-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis (3-hydroxyethyl) -para-phenylenediamine, 4-N, N-bis (3hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (B-hydroxyethyl) amino-2chloroanilineja 2-3-hydroxyethyl-para- phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (3-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, Ndimethyl-3-methyl-para-phenyl enenediamine, N-ethyl-N- (3-hydroxyethyl) para-phenylenediamine, N- (3, Y-dihydroxypropyl) -para-phenylenediamine, N- (4'-aminophenyl) -para-phenylenediamine, N- phenyl-paraphenylenediamine, 2-3-hydroxyethyloxy-para-phenylenediamine, 2-βacetylaminoethyloxy-para-phenylenediamine, N- (3-methoxyethyl) -paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-paraphenylen 3-hydroxyethylamino-5-aminotoluene and 3-hydroxy1- (4'-aminophenyl) pyrrolidine and the corresponding addition salts with an acid.

Among the aforementioned para-phenylenediamines, particularly preferred are para-phenylenediamine, para-toluenediamine, 2-isopropyl-paraphenylenediamine, 2-3-hydroxyethyl-para-phenylenediamine, 2-βhydroxyethyloxy-para-phenylenediamine, 2 , 6-dimethyl-paraphenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethylpara-phenylenediamine, N, N-bis (3-hydroxyethyl) -para-phenylenediamine, 2-chloro-para- phenylenediamine and 2-3-acetylaminoethyloxy-paraphenylenediamine and the corresponding addition salts with an acid.

According to a particular embodiment, the base (s) of additional oxidation (s) is (are) chosen (s) from bis (phenyl) alkylenediamines, more particularly chosen (s) from N, N'-bis (3-hydroxyethyl) -N, N'-bis (4'aminophenyl) -1,3-diaminopropanol, N, N'-bis (3-hydroxyethyl) -N, N'-bis (4'aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (3-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 and 1,8-bis (2,5diaminophenoxy) -3,6-dioxaoctane and the corresponding addition salts.

According to a particular embodiment the base (s) of additional oxidation (s) is (are) chosen (s) from para-aminophenols, more particularly chosen (s) from para-aminophenol, 4-amino -3methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4 amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2hydroxymethylphenol, 4-amino-2 -methoxymethylphenol, 4-amino-2aminomethylphenol, 4-amino-2- (3-hydroxyethylaminomethyl) phenol and 4 amino-2-fluorophenol and the corresponding addition salts with an acid.

According to a particular embodiment, the base (s) of additional oxidation (s) is (are) chosen (s) from ortho-aminophenols, more particularly chosen (s) from 2-aminophenol, 2-amino -5methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol and the corresponding addition salts.

According to a particular embodiment the base (s) of additional oxidation (s) is (are) chosen (s) from heterocyclic bases more particularly those derived from pyridine, pyrimidine and pyrazole different from the compound (s) of formula (I) defined above.

Among the pyridine derivatives which may be mentioned, there are the compounds for example described in the patents GB 1 026 978 and GB 1 153 196, for example 2,5-diaminopyridine, 2- (4methoxyphenyl) amino-3-aminopyridine and 3,4-diaminopyridine and the corresponding addition salts.

Other oxidation bases derived from pyridine which are useful in the present invention are the oxidation bases for 3-aminopyrazolo [1,5a] pyridine or the corresponding addition salts described, for example, in the patent application FR 2 801 308. We can for example cite pyrazolo [1,5a] pyrid-3-ylamine, 2-acetylaminopyrazolo [1,5-a] pyrid-3-ylamine, 2morpholin-4-ylpyrazolo [1,5 -a] pyrid-3-ylamine, 3-aminopyrazolo [1,5a] pyridine-2-carboxylic acid, 2-methoxypyrazolo [1,5-a] pyrid-3-ylamine, (3aminopyrazolo [1,5 -a] pyrid-7-yl) methanol, 2- (3-aminopyrazolo [1,5-a] pyrid-5yl) ethanol, 2- (3-aminopyrazolo [1,5-a] pyrid-7-yl ) ethanol, (3aminopyrazolo [1,5-a] pyrid-2-yl) methanol, 3,6-diaminopyrazolo [1,5a] pyridine, 3,4-diaminopyrazolo [1,5-a] pyridine, pyrazolo [1,5-a] pyridine3,7-diamine, 7-morpholin-4-ylpyrazolo [1,5-a] pyrid-3-ylamine, pyrazolo [1,5-a] pyridine-3,5- diamine, 5-morpholin-4-ylpyrazolo [1,5-a] pyrid-3ylamine, 2 - [(3-aminopyrazolo [1,5-a] pyrid-5-yl) (2-hydroxyethyl) amino] ethanol, 2 - [(3-aminopyrazolo [1,5-a] pyrid-7-yl) (2hydroxyethyl) amino] ethanol, 3-aminopyrazolo [1, 5-a] pyridin-5-ol, 3aminopyrazolo [1,5-a] pyridin-4-ol, 3-aminopyrazolo [1,5-a] pyridin-6-ol, 3aminopyrazolo [1,5-a ] pyridin-7-ol, 2-3-hydroxyethoxy-3-amino-pyrazolo [1,5a] pyridine; 2- (4-dimethylpiperazinium-1-yl) -3-amino-pyrazolo [1,5a] pyridine; and the corresponding addition salts.

More particularly, the additional oxidation bases derived from pyridine which are useful in the present invention are chosen from

3-aminopyrazolo- [1,5-a] -pyridines and preferably substituted on the carbon atom 2 by:

a) a (di) (Ci-C6) (alkyl) amino group, said alkyl group being able to be substituted by at least one hydroxy, amino, imidazolium group;

b) a heterocycloalkyl group containing 5 to 7 members and 1 to 3 heteroatoms, optionally cationic, optionally substituted by one or more (C-i-C6) alkyl groups, such as a di (Ci-C4) alkylpiperazine group; or

c) an (C-i-C6) alkoxy group optionally substituted by one or more hydroxy groups such as a β-hydroxyalkoxy group and the corresponding addition salts.

Among the pyrimidine derivatives which may be mentioned, there are the compounds described, for example, in patents DE 2359399; JP 88169571; 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 their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

Among the pyrazole derivatives different from the compounds of formula (I) of the invention, and which can be used as additional oxidation base which may be mentioned, there are the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FRA-2 733 749 and DE 195 43 988, such as 4,5-diamino-1methylpyrazole, 4,5-diamino-1- (3-hydroxyethyl) pyrazole, 3, 4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4, 5-diamino-1methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-fe / ï -butyl-1-methylpyrazole, 4,5-diamino-1-fe / Î-butyl-3-methylpyrazole, 4,5-diamino-1- (3hydroxyethyl) -3-methylpyrazole, 4,5-diamino- 1-ethyl-3-methylpyrazole, the

4.5- diamino-1 -ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1 -ethyl-3hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole,

4.5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1 3060002 isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole,

3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1methyl-4-methylaminopyrazole, 3,5-diamino-4- (3-hydroxyethyl) amino- 1 methylpyrazole and the corresponding addition salts. It is also possible to use 4,5-diamino-1- (3-methoxyethyl) pyrazole.

A 4,5-diaminopyrazole will be used preferably and even more preferably 4,5-diamino-1- (3-hydroxyethyl) pyrazole and / or a corresponding salt.

The pyrazole derivatives different from the compounds of formula (I) of the invention, and usable as an additional oxidation base which may also be mentioned include diamino - / \ /, / \ / - dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and the corresponding addition salts: 2,3diamino-6,7-dihydro-1 H, 5H-pyrazolo [1,2-a] pyrazol- 1-one, 2-amino-3ethylamino-6,7-dihydro-1 H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3isopropylamino-6,7-dihydro-1 H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino3- (py rrol idin-1 -yl) -6,7-dihydro-1 H, 5H-pyrazolo [1,2- a] pyrazol-1 -one, 4,5diamino-1,2-dimethy 1-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethy 1-1,2dihydropyrazol-3- one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2dihydropyrazol-3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1 H, 5Hpyrazolo [1,2-a] pyrazol-1 -one, 2-amino-3-dimethylamino-6,7-dihydro-1 H, 5Hpyrazolo [1,2-a] pyrazol-1 -one, l a 2,3-diamino-5,6,7,8-tetrahydro-1 H, 6Hpyridazino [1,2-a] pyrazol-1 -one, 4-amino-1,2-diethyl-5- (pyrrolidin- 1 -yl) -1,2dihydropyrazol-3-one, 4-amino-5- (3-dimethylaminopyrrolidin-1 -yl) -1,2diethyl-1,2-dihydropyrazol-3-one, 2,3-diamino -6-hydroxy-6,7-dihydro1 H, 5H-pyrazolo [1,2-a] pyrazol-1 -one.

Preferably, 2,3-diamino-6,7-dihydro-1 H, 5H-pyrazolo [1,2a] pyrazol-1 -one and / or a corresponding salt will be used.

Preferably, 4,5-diamino-1- (3-hydroxyethyl) pyrazole, 4,5diamino-1- (hexyll) prazole and / or 2,3-diamino-6,7-dihydro-1 H, 5Hpyrazolo will be used. [1,2-a] pyrazol-1-one and / or a corresponding salt as heterocyclic bases.

The composition according to the invention may optionally comprise iii) one or more coupling agents advantageously chosen from those traditionally used in the coloring of keratin fibers.

Among these coupling agents, mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents as well as the corresponding addition salts.

Mention may, for example, be made of 1,3-dihydroxybenzene, 1,3-dihydroxy2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (B10 hydroxyethyloxy) benzene, 2- amino-4- (B-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane,

3- ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 1-βhydroxyethylamino-3,4-methylenedioxybenzene, Ι'α-naphthol, 2-methyl-1naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino2,6-dimethoxypyridine, 1 -N- (B-hydroxyethyl) amino-3,4- methylenedioxybenzene, 2,6-bis (B-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3methylpyrazol-5 -one, 2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole, 2,620 dimethyl [3,2-c] -1,2,4-triazole and 6-methylpyrazolo [1 , 5-a] benzimidazole, 2methyl-5-aminophenol, 5-N- (B-hydroxyethyl) amino-2-methylphenol, 3 aminophenol, 3-amino-2-chloro-6-methylphenol, the salts of corresponding addition with an acid and the corresponding mixtures.

More particularly the coupling agent (s) of the invention is (are) chosen (s) from the compounds of formula (II) and (II ’):

As well as their acid or base salts, organic or mineral, and their solvates such as hydrates;

Formulas (II) and (II ’), in which:

- X-ι, and X ₂ , identical or different, represent a group chosen from hydroxy, (di) (Ci-C6) (alkyl) amino, (di) hydroxy (Ci-C6) alkylamino;

- Y represents a hydrogen atom, (Ci-Ce) (hydroxy) alkyl, or then two adjacent substituents Y and Xi and / or Y and X ₂ form together with the carbon atoms which carry them an optionally substituted heterocycle group, such as morpholinyl, piperazinyl, piperidinyl preferably a hydrogen atom, (Ci-C6alkyl, or then two adjacent substituents Y and Xi form together with the carbon atoms which carry them a morpholinyl group optionally substituted by a group (Ci-C4 ) alkyl;

- p is 1,2, 3 or 4;

- t is 1,2 or 3;

It being understood that when p or t is greater than or equal to 2 the groups Y are identical or different from each other.

More particularly, the coupling agent (s) of the invention is (are) chosen from the compounds of formula (ll _a ) and (ll ' _a ):

As well as their acid or base salts, organic or mineral, and their solvates such as hydrates;

Formulas (lla) and (ll’a) in which:

- Xi and X ₂ are as defined above, preferably Xi and / or X ₂ represents (s) a hydroxy, amino, or (hydroxy) alkylamino group;

- Yi represents a hydrogen atom or a group (Ci-C6alkyl;

- Y ₂ represents a hydrogen atom, or forms with the substituent Y ₂ an optionally substituted heterocycle, such as morpholinyl, piperazinyl, piperidinyl preferably morpholinyl optionally substituted by a (Ci-C4) alkyl group.

Preferably the coupler (s) of the invention are chosen from: 2methylresorcinol, 6-hydroxy benzomorpholine; 2-amino-3-hydroxypyridine; 25 ({3 - [(2-hydroxyethyl) amino] -2-methylphenyl} amino) ethanol as well as their acid or base salts and their solvates such as hydrates.

In general, the addition salts of oxidation bases and of coupling agents which can be used in the context of the invention are in particular chosen from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base (s) each represents (s) advantageously 0.001% to 10% by weight relative to the total weight of the composition and preferably 0.005% to 5% by weight relative to the total weight of the composition and ready-to-use composition.

The coupling agent (s), if they are (are) present, each represents (s) advantageously 0.001% to 10% by weight relative to the total weight of the composition and preferably 0.005 % to 5% by weight relative to the total weight of the composition and of the ready-to-use composition.

The composition according to the invention may optionally comprise iv) one or more direct synthetic or natural dyes, chosen from anionic and nonionic species, preferably cationic or nonionic species,

Examples of suitable direct dyes which may be mentioned include azo direct dyes; (poly) methine dyes such as cyanines, hemicyanins and styryles; carbonyl dyes; azine dyes; nitro (hetero) aryl dyes; tri (hetero) arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

The direct dyes are preferably cationic direct dyes. Mention may be made of the cationic hydrazono dyes of the formulas (Ilia) and (IIIa), the cationic dyes azo (IVa) and (IV’a) and the cationic dyes diazo (Va) below:

Het ⁺ -C (R ^a ) = NN (R ^b ) -Ar, An 'Het ⁺ -N (R ^a ) -N = C (R ^b ) -Ar, An' Het ⁺ -N = N-Ar, An (Ilia) (lll'a) (IVa)

Ar ⁺ -N = N-Ar ”, An 'and Het ⁺ -N = N-Ar'-N = N-Ar, An (IV'a) (Va) in which formulas (Ilia), (lll'a) , (IVa), (IV'a) and (Va):

• Het ⁺ represents a heteroaryl cationic radical, preferably carrying an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted, preferably, by one or more (Ci-Cs) -alkyl groups, such as methyl;

· Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, carrying an exocyclic cationic charge, preferably ammonium, in particular tri (Ci-C8) alkylammonium such as trimethylammonium;

Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferably by one or more electron donor groups, such as i) (Ci-Cs) optionally substituted alkyl, ii) (Ci-Csjalkoxy optionally substituted, iii) (di) (CiCsKalkyljamino optionally substituted on the alkyl group (s) by a hydroxyl group, iv) aryl (Ci-C8) alkylamino, v) / V- (Ci-Cs) alkyl - / \ / aryl (Ci-C8) optionally substituted alkylamino or, alternatively, Ar represents a julolidine group;

• Ar 'represents an optionally substituted divalent (hetero) arylene group, such as phenylene, in particular para-phenylene, or naphthalene, which are optionally substituted, preferably by one or more (Ci-Cs) alkyl, hydroxyl or (Ci -Csjalcoxy;

· Ar ”represents an optionally substituted (hetero) aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferably by one or more (Ci-Cs) alkyl, hydroxyl, (di) (Ci-C8) (alkyl) groups ) amino, (C 1 -C 6 alkoxy or phenyl;

• R ^a and R ^b , which may be the same or different, represent a hydrogen atom or a group (Ci-Csjalkyle, which is optionally substituted, preferably by a hydroxyl group;

or, alternatively, the substituent R ^a with a substituent of Het ⁺ and / or R ^b 5 with a substituent of Ar and / or R ^a with R ^b form, together with the atoms which carry them, a (hetero) cycloalkyl;

in particular, R ^a and R ^b represent a hydrogen atom or a (Ci-C4) alkyl group, which is optionally substituted by a hydroxyl group;

· An 'represents an anionic counterion, such as mesylate or halide.

Mention may in particular be made of the cationic azo and hydrazono dyes carrying an endocyclic cationic charge of the formulas (Ilia), (IIIa) and (IVa) as defined above. More particularly, those of formulas (Ilia), (IIIa) and (IVa) derived from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

Preferably, the cationic part is derived from the following derivatives:

(llla-1) (IVa-1) formulas (111-1) and (IV-1) with:

- R ¹ representing a (Ci-C4) -alkyl group such as methyl;

- R ² and R ³ , which are identical or different, represent a hydrogen atom or a (Ci-C4) -alkyl group, such as methyl; and

- R ⁴ represent a hydrogen atom or an electron donor group, such as an optionally substituted (Ci-Cs) alkyl group, (Ci-Cs) optionally substituted alkoxy or (di) (Ci-C8) (alkyl ) amino optionally substituted on the alkyl group (s) by a hydroxyl group; in particular R ⁴ represents a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferably CH;

- An 'represents an anionic counterion, such as mesylate or halide.

In particular, the dye of the formulas (IIIa-1) and (IVa-1) is chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or corresponding derivatives:

Basic Red 51

Basic Orange 31

Basic Yellow 87

An 'represents an anionic counterion, such as mesylate or halide.

Among the natural direct dyes which can be used according to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, io protocatechaldehyde, 'indigo, isatin, curcumin, spinulosin, apigenidine and orcein. Extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna can also be used.

When they are present, the direct dye (s) iv) more particularly represent 0.001% to 10% by weight and preferably 0.005% to 5% by weight of the total weight of the composition.

The medium suitable for dyeing (or support) used according to the invention consists of water or of a mixture of water and at least one organic solvent chosen from lower C1-C4 alkanols, polyols and polyol ethers, aromatic alcohols, analogues and their mixtures.

The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative anionic, cationic, nonionic and amphoteric polymeric thickeners, antioxidant agents, penetration 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 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 in dyeing keratin fibers or even using conventional buffer systems.

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

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (V) below:

R _r r

6 \

N WN (V) /

R ₇ ^Z r ₉

Formula (V) in which W is a linear or branched (Ci-C6) alkylene group, in particular propylene, optionally substituted by one or more hydroxy groups; R ₆ , R7, Rs and R9, identical or different, represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged.

The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.

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

According to this method, at least one dye composition as defined above is applied to the fibers, for a time sufficient to develop the desired coloration, either in air or using an oxidizing agent. The dye 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 coloring of the fibers can be carried out without the addition of an oxidizing agent, only in contact with the 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 pH, neutral or alkaline using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.

According to this second form of implementation of the dyeing process of the invention, the dye composition described above is preferably mixed with an oxidizing composition containing, in an environment suitable for dyeing, at the time of use, at least one oxidizing agent present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibers and left to stand for 3 to 50 minutes, preferably 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 the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids, oxidase enzymes among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

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

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

The composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels, foams, or in any other form suitable for dyeing keratin fibers, and in particular human hair.

Another subject of the invention is the use of one or more compound (s) of formula (I), (I '), or (I ”) as defined above, optionally in the presence of additional oxidation base (s) as defined above, and optionally in the presence of one or more couplers as defined above, and optionally in presence of oxidizing agent (s) in particular as defined above, for dyeing keratin fibers, in particular human fibers such as the hair.

Preferably, the use of one or more compound (s) of formula (I), (I '), 5 or (I ”) as defined above, in the presence of one or more couplers ( s) as defined above, and in the presence of oxidizing agent (s) in particular as defined above, for dyeing keratin fibers, in particular human fibers such as the hair.

Another object of the invention is a multi-compartment device or dye kit or any other multi-compartment packaging system, a first compartment of which contains the dye composition as defined above and a second compartment of which contains an oxidizing composition. These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

EXAMPLES

Example 1: Synthesis of / V- [5- (4 _l 5-diamino-1 / - / - pyrazol-1vDpentvIlacetamide hydrochloride, compound 11

Synthesis of the amino / V-protected aldehyde reagent 4

2 3 3 '4

Step i

136 g of aminopentanol (1) and 1.3 liters of toluene are added to a 2 liter three-necked reactor, comprising a magnetic stirrer, a thermometer, a condenser and a Dean-Starck, under an inert atmosphere (nitrogen). added to the solution 174.2 g of acetophenone and 25 g of para-toluene sulfonic acid.

The mixture is heated at reflux for 24 hours, removing the water formed with Dean-Starck.

The reaction is followed by proton NMR until 90% conversion.

After the reaction medium has cooled, the organic phase is washed twice with water and dried over magnesium sulfate.

After removing the salts by filtration, the juices are concentrated under vacuum until a brown oil corresponding to the expected compound (2) is obtained. The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Step ii

51.5 g of lithium aluminum hydride (LiAIH) are suspended in a 2 liter three-necked reactor, equipped with magnetic stirring, a thermometer, a condenser, under an inert atmosphere (nitrogen). ₄ ) in 1.3 liters of tetrahydrofuran then the compound (2) is introduced over 1 hour 30 minutes and the reaction is continued overnight.

After cooling to 0 ° G of the reaction medium, a 5 M solution of sodium hydroxide is added dropwise with stirring over 2 hours. The medium is filtered through a bed of celite, rinsed with ethyl acetate. The filtrate is partially concentrated to remove the tetrahydrofuran and the organic phase is washed with twice with saturated sodium chloride solution, then twice with water, dried over magnesium sulfate.

After removing the magnesium sulphate salts by filtration, the juices are concentrated under vacuum until an orange oil corresponding to the expected compound (3) is obtained. The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Step iii

160 g of compound (3) in 1.6 liters of tetrahydrofuran and then 230, are added to a 2 liter three-necked reactor, equipped with magnetic stirring, a thermometer, a condenser, under an inert atmosphere (nitrogen), 5 g of di-tert-butyl dicarbonate (tBu-OC (O) -OC (O) O-tBu or BOC2O) and 147 ml of trimethylamine. The reaction medium is stirred for 2 days at room temperature before being concentrated and then taken up in ethyl acetate. The organic phase is washed with a saturated solution of sodium chloride and then dried over magnesium sulfate, concentrated under vacuum before being purified by column of silica with a heptane-ethyl acetate mixture to yield 118.3 g of orange oil (3 ') corresponding to the expected compound. Spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound

Step iv

A solution of 73.2 g of oxalyl chloride in 600 ml of dichloromethane is added to a 2 liter three-necked reactor, equipped with mechanical stirring, a thermometer, a condenser, under an inert atmosphere (nitrogen). . With stirring, this solution is cooled to -78 ° C and dropwise, 118.3 g of the compound (3 ’) are added over 1 hour.

After 20 minutes of stirring, 101.4 of the trimethylamine are added dropwise and the reaction medium is poured onto ice water. The organic phase is washed with a saturated sodium chloride solution, concentrated, then the residue is taken up in ethyl acetate, and the organic phase is washed with a saturated sodium chloride solution. After drying over magnesium sulphate, the organic phase is concentrated and purified on a silica column with a heptane-ethyl acetate mixture 8/2 to yield a yellow oil corresponding to the expected amino / V-protected aldehyde compound (4).

Spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound

Synthesis of compound 11 from the amino / V-protected aldehyde compound 4:

Step v

25 ml of / V-propanol and 3.12 g d are added to an three-necked reactor, equipped with magnetic stirring, a thermometer, a condenser and a dropping funnel. hydrazine hydrates and at 0 ° C

3.78 g of acrylonitrile and stirring is continued for 30 minutes before adding dropwise a solution of 20 g of the aldehyde (4) dissolved in 15 ml of / V-propanol at room temperature. After one hour of reaction, the medium is concentrated to yield a yellow oil corresponding to the expected compound (5). The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Step vi

In a trico reactor! 500 ml, equipped with mechanical stirring, a thermometer, a condenser and a dropping funnel, a 20.8 g solution of the compound (5) obtained is introduced under an inert atmosphere (nitrogen). the previous step in 230 ml of tert-butanol and 7.11 g of potassium ter-butoxide at room temperature. The environment reacts! is brought to reflux for 1 hour.

After cooling, the solvent is concentrated in vacuo and the crude is taken up in ethyl ether.

The organic phase is washed with a saturated solution of sodium chloride, dried over magnesium sulfate, and concentrated in vacuo to yield an orange oil corresponding to the expected compound (6). Spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound

Step vii

In a three-necked 100 ml reactor, equipped with mechanical stirring, a thermometer, a condenser and a dropping funnel, a solution of 19.12 g of compound (6) is introduced under nitrogen into 130 ml of ethanol and 7.81 g of amyl nitrite are added at 0 ° C. over 5 minutes followed by a solution of 17 ml of concentrated hydrochloric acid in 35 m! ethylene glycol.

It is maintained for 30 minutes at room temperature and 30 minutes at reflux before concentrating in vacuo and resuming in water. The medium is extracted 3 times with diisopropyl ether and the aqueous phase is basified to pH = 11 with concentrated ammonia. The basic solution is extracted 4 times with dichloromethane

The combined organic phases are washed with a saturated solution of sodium chloride, dried over magnesium sulfate, and concentrated in vacuo to yield a black oil corresponding to the expected compound (7).

The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Step viii

A 500 ml three-necked reactor, equipped with mechanical stirring and a thermometer, is introduced under an inert atmosphere (nitrogen).

14.9 g of compound (7), 12.3 g of hydrazine in 300 ml of methanol and 4.6 g of 10% palladium on carbon. The mixture is brought to reflux for 30 minutes and after cooling and elimination of the catalyst on celite, the filtrate is concentrated to yield a black oil corresponding to the expected compound (8). The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Step ix

Into an inert atmosphere (nitrogen), a solution of 12.46 g of compound (8), 10.85 g of hydrazine hydrate in 250 is introduced into a 300 ml flask equipped with magnetic stirring and a condenser. ml of ethanol and 4 g of 10% palladium on carbon. The reaction medium is brought to reflux overnight and after cooling and elimination of the catalyst on celite, washed with methanol. The solvent is evaporated to the maximum and the crude is taken up in water. The aqueous phase is lyophilized to yield an orange oil corresponding to the expected compound (9). The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Step x

3.93 g of compound (9), 100 ml of acetic acid are added to an 250 ml flask equipped with magnetic stirring and a condenser, under an inert atmosphere (nitrogen), and 28.58 are added. g of acetic anhydride. The reaction medium is stirred at room temperature for 5 hours then concentrated and purified on a column of silica gel (eluent dichloromethane / methanol / 32% ammonia: 9/1/1).

After removing the solvent, the residue is taken up in ethyl ether to yield an orange powder corresponding to the expected compound (10).

The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Step xi: Synthesis of t'i-fi-dô-diamino-1H-pyrazol-lyl) pentyl] acetamide hydrochloride

3.93 g of compound 10, 70 ml of ethanol and 70 ml of hydrochloric isopropanol 5 are introduced into an 200 ml flask equipped with magnetic stirring and a condenser, under an inert atmosphere (nitrogen), 5 M. The reaction mixture is brought to reflux for 5 hours, then the solvent is removed in vacuo on a rotary evaporator. The crude product obtained is taken up with isopropanol and then precipitated with isopropyl ether. The white precipitate formed is recovered on a frit, washed with isopropyl ether before being dried under vacuum at 40 ° C in the presence of P ₂ Os to constant weight. A white powder corresponding to the expected compound (11) is thus isolated. The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Example 2 Synthesis of 1- (5-aminopentyl) hydrochloride -1 / - / - pyrazole-4 _l 5diamine

Step xii:

0.77 g of the compound of example 1, compound 11, 16 ml of hydrochloric acid are introduced into a 100 ml flask equipped with magnetic stirring and a condenser, under an inert atmosphere (nitrogen). 37% and 33 ml of ethanol. The reaction mixture is brought to reflux for several days, the reaction is followed by NMR.

At the end of the reaction, the solvent is removed in vacuo on a rotary evaporator. The crude product obtained is taken up with isopropanol and then precipitated with isopropyl ether, filtered through a frit and then washed again with isopropyl ether before being dried under vacuum at 40 ° C. in the presence of P ₂ Os to constant weight. . A beige powder is thus isolated corresponding to the expected compound (12). The spectroscopic and spectrometric analyzes are in agreement with the structure of the expected compound.

Example 3 Synthesis of 1- (5-aminopentvl) -3-methvl-1H-pyrazole5 4,5-diamine sulfate diagram 2: For the compounds of formula (I) in which Ri and R ₂ represent a group (Ci- C6) alkyl, or (C2-C4) alkenyl, linear or branched, preferably (Ci-C4) alkyl such as such as methyl:

methyl and R represents an ALK group

^{1 2a}

diagram above in which R 'represents a (Ci-C6alkyl such as methyl, aryl (Ci-Ce) alkyl such as benzyl or phenyl-CH (CH ₃ ) -.

To synthesize the compound 4a, steps i ', ii', and iii 'are carried out according to the operating method described in steps iii and iv respectively of example 1 without passing through steps i and ii with R' as defined previously.

step v ’

25 ml of / V-propanol and 3.1 g of hydrazine hydrate are introduced under nitrogen into a three-necked reactor, equipped with magnetic stirring, a thermometer, a condenser and a dropping funnel. after cooling to 0 ° C, 3.78 g of crotonitrile. Stirring is continued for 30 minutes at 0 ° C., then 20 g of the aldehyde (4a) previously dissolved in 15 ml of / V-propanol at room temperature are added dropwise. After one hour of reaction, the medium is concentrated to yield a yellow oil corresponding to the expected compound (5a).

Step vi ’

22.93 g of the compound (5a) dissolved in 230 are introduced into nitrogen in a 500 ml three-necked reactor, equipped with mechanical stirring, a thermometer, a condenser and a dropping funnel ml of tert-butanol, then, at room temperature, 6.66 g of potassium ter-butoxide. The reaction medium is brought to reflux for 40 minutes. After cooling, the medium is concentrated in vacuo and the crude is taken up in ethyl ether. The organic phase is washed with a saturated solution of sodium chloride, dried over magnesium sulphate, the ester is eliminated with a rotary evaporator to yield an orange oil corresponding to the expected compound (6a).

Step vii ’

In a three-necked 100 ml reactor, equipped with mechanical stirring, a thermometer, a condenser and a dropping funnel, a solution of 17.64 g of the compound (6a) is introduced under nitrogen. 100 ml of ethanol and, after cooling to 0 ° C., 6.95 g of amyl nitrite are added over 5 minutes, then a solution of 15.7 ml of concentrated hydrochloric acid in 30 ml of ethylene glycol.

The medium is then kept stirring for 30 minutes at room temperature and then 30 minutes at reflux before being cooled and concentrated in vacuo then taken up in water, and extracted 3 times with diisopropyl ether. The pH of the aqueous phase is adjusted to pH = 10 with concentrated ammonia and the aqueous phase is then extracted 4 times with dichloromethane. The combined organic phases are washed with a saturated solution of sodium chloride, dried over magnesium sulfate and then concentrated in vacuo to yield a black oil corresponding to the expected compound (7a).

Step viii ’

11.46 g of compound (7a) and 9 g of hydrazine hydrate in 230 ml of methanol and then 3.3 g are introduced under nitrogen into a 500 ml three-necked reactor equipped with mechanical stirring and a thermometer. g of 10% palladium on charcoal. The best reaction is brought to reflux for 30 minutes and after cooling and elimination of the celite catalyst, the filtrate is concentrated to yield a black oil corresponding to the expected compound (8a).

Step ix ’

A solution of 13.02 g of compound (8a), 10.08 g of hydrazine hydrate in 260 ml of is introduced into a 300 ml flask equipped with magnetic stirring and a condenser. ethanol and 4 g of 10% palladium on charcoal. The best reaction is brought to reflux overnight and after cooling and removal of the celite catalyst, washed with methanol. The solvent is evaporated to the maximum and the crude is taken up in water. The aqueous phase is lyophilized to yield an orange oil corresponding to the expected compound (9a).

Step x ’

4.76 g of the compound (9a), 50 ml of ethanol are added under nitrogen into a 100 ml flask equipped with magnetic stirring, a condenser and a dropping funnel. 96 ml of 1 M sulfuric acid at 0 ° C.

The precipitate formed is stirred for 30 minutes then isolated by filtration, rinsed with ethanol. The combined organic phases are lyophilized, an orange powder is isolated corresponding to the expected compound (10).

Example 4 Synthesis of 1- [5- (dimethylamino) pentvH-1 / - / pyrazole-4,5-diamine hydrochloride (32)

General procedure

2b 3b 4b 5b (21) (23) (24) (25)

NO

Step 1-a

50 g of 5-aminopentanol 1 'in a mixture of 250 ml of dioxane and 250 ml of ethanol are introduced under nitrogen into a 500 ml three-necked reactor equipped with magnetic stirring and a thermometer. at room temperature 117 g of BOC2O while controlling the temperature. The reaction is kept under stirring for 20 hours. The dioxane is then removed by evaporation and the aqueous phase is extracted three times with ethyl acetate. The combined organic phases are washed with a saturated solution of sodium chloride, dried over magnesium sulfate, and the solvents are removed in vacuo to yield a yellow oil corresponding to the expected compound (2b).

Step 1-b

A 98 g suspension of 98 g hydride is introduced under nitrogen into a 2 liter three-necked reactor, equipped with magnetic stirring and a thermometer.

Lithium aluminum LiAIH ₄ in 1 liter of tetrahydrofuran, and 105 g of (21) in 200 ml of tetrahydrofuran are added dropwise over 20 minutes.

The reaction medium, with stirring, is brought to 80 ° C. for 3 hours then cooled to 5 ° C. and 98 ml of water are added dropwise over 1 hour 30 minutes. The suspension thus obtained is cooled to 0 ° C and 98 ml of 20% sodium hydroxide are added and stirring is continued overnight. After adding 280 ml of water, the reaction medium is filtered through celite, rinsed with ethyl acetate and the filtrate is concentrated in vacuo to yield a yellow oil corresponding to the expected compound (3b).

Step1-c

102.6 g of BoC ₂ O in 600 ml of tetrahydrofuran, then 50 g of compound (3b) and 65 ml, are introduced under nitrogen into a 2-liter three-necked reactor, equipped with magnetic stirring and a thermometer. triethylamine. This medium is stirred for 20 hours then added with 500 ml of water and the aqueous phase is extracted three times with ethyl acetate. The combined organic phases are washed with a saturated solution of sodium chloride, dried over magnesium sulfate, and the solvents are removed in vacuo to yield a yellow oil corresponding to the expected compound (4b).

Step1-d

To a solution of 36.8 ml of oxalyl chloride in 400 ml of dichloromethane in a three-liter 1 liter reactor, equipped with magnetic stirring and a thermometer, is added under nitrogen and dropwise at -78 ° C a solution of (4b) in 100 ml of dichloromethane. Stirring is continued for 30 minutes at -78 ° C. and 197 ml of triethylamine and then 500 ml of water are added. The aqueous phase is extracted three times with ethyl acetate and the combined organic phases are washed with a saturated solution of sodium chloride, dried over magnesium sulfate, then the solvents are removed under vacuum to yield a corresponding yellow oil to the expected compound (5b).

Step-e

In a three-necked reactor, equipped with a magnetic stirrer, a thermometer, a condenser and a dropping funnel, 60 ml of

N-propanol and 4.4 hydrazine hydrate, then at 0 ° C, 4.93 g of acrylonitrile. Stirring is continued for 30 minutes and then a solution of 20 g of (5b) in 20 ml of N-propanol is added dropwise at room temperature. After one hour of reaction, the medium is concentrated under vacuum to yield a yellow oil corresponding to the expected compound (6b).

Step-f

20.8 g of (6b) in 208 ml are introduced into nitrogen in a 500 ml three-necked reactor, equipped with mechanical stirring, a thermometer, a condenser and a dropping funnel. of tert-butanol then 8.27 g of potassium ter-butoxide. The reaction medium is brought to 80 ° C. for 30 minutes, then, after cooling, the solvent is removed in vacuo and the crude is taken up in ethyl acetate. The organic phase is washed with a saturated solution of sodium chloride then dried over magnesium sulphate, and concentrated under vacuum to yield 19.1 g of crude, isolated in the form of orange oil which is purified on a silica column (eluent dichloromethane / methanol (98/2)) to provide an oil corresponding to the expected compound (7b).

Step-g

A nitrogen-containing suspension of 7.9 g of lithium aluminum hydride is introduced into a 1 liter three-necked reactor, equipped with mechanical stirring, a thermometer, a condenser and a dropping funnel. (LiAIH ₄ ) in 400 ml of tetrahydrofuran, then a solution of compound (7b) is poured dropwise at 0 ° C. in 100 ml of tetrahydrofuran. The mixture is brought to 80 ° C. for 3 hours and after cooling to 0 ° C., the medium is carefully poured onto a solution of sodium hydroxide concentrated at 0 ° C.

After 30 minutes with stirring at room temperature, a precipitate appears which is separated by filtration, rinsed with tetrahydrofuran, the tetrahydrofuran filtrate is dried over magnesium sulphate, the solvents are eliminated on a rotary evaporator to yield an orange oil corresponding to the expected compound (8b ).

Step 1-h

12.1 g of the compound (8b) are introduced into 164 ml in a three-necked 100 ml reactor, equipped with mechanical stirring, a thermometer, a condenser and a dropping funnel. ethanol and 9.38 g of isopentyl nitrite are added at 5 ° C. over 5 minutes and finally 5.7 ml of concentrated hydrochloric acid in 18 ml of dimethoxyethane are added. The medium is stirred 30 minutes at 0 ° C and 30 minutes at room temperature then concentrated in vacuo and taken up in water, extracted three times with di-isopropyl ether. The pH of the aqueous phase is adjusted to pH = 10 with concentrated ammonia. The basic aqueous phase is extracted 4 times with dichloromethane and the combined organic phases are washed with a saturated solution of sodium chloride, dried over magnesium sulfate, concentrated in vacuo, to yield a black gum corresponding to the expected compound (9b).

Step 1-i

To a solution of 9.55 g of the compound (9b), 10.6 g of hydrazine hydrate in 200 ml of methanol in a 500 ml three-necked flask equipped with magnetic stirring, a thermometer and a introduced, 3.94 g of palladium on carbon at 10% The best reaction is brought to reflux for 30 minutes and after cooling and elimination of the catalyst on celite, the filtrate is concentrated in vacuo to yield a black gum corresponding to the expected compound (10b).

Step 1-i

4.33 g of the compound (10b), 100 ml of acetic acid and 8.37 g of anhydride are added to a 250 ml flask equipped with magnetic stirring and a condenser. acetic. The reaction medium is stirred at room temperature for 2 hours then concentrated under vacuum and the residue obtained is purified on a column of silica gel (eluent dichloromethane / methanol / 32% ammonia 9/1 / 0.02), followed by evaporation and lyophilization leading to a red solid corresponding to the expected compound (11b).

Step 1-i

Synthesis of N- [5- (4,5-diamino-1H-Dvrazol-1-yl) hentvnacetamide hydrochloride

1.4 g of the compound (11b), 26 ml of 37% hydrochloric acid and 44 ml of ethanol are introduced into a 250 ml flask equipped with magnetic stirring and a condenser. The reaction mixture is brought to reflux for several days, the reaction is followed by NMR.

At the end of the reaction, the solvent is removed in vacuo on a rotary evaporator. The crude product obtained is taken up with isopropanol and then precipitated with isopropyl ether. The white precipitate formed is recovered on a frit, washed with isopropyl ether, and dried under vacuum at 40 ° C in the presence of P ₂ Os to constant weight. A white powder corresponding to the expected compound (12b) is thus isolated.

DYE EXAMPLES

The following dye support (pH 9.5) was produced:

ingredients quantity 96 ° ethyl alcohol 20.8 g Sodium metabisulfite in 35% aqueous solution 0.23 g M.A * Pentasodium salt of diethylene triamine pentaacetic acid in 40% aqueous solution 0.48 g M.A * Cs-C-iopolyglucoside alkyl in 60% aqueous solution 3.6 g M.A * Benzyl alcohol 2.0 g Polyethylene glycol with 8 ethylene oxide units 3.0g NH ₄ CI 4.32 g Ammonia at 20% NH ₃ 2.94 g Demineralized water q.s.p. 100g

*MY. corresponds to the active ingredient

To this dye support is added the oxidation dyes as described in Tables 1 to 3 below.

At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained.

io Each mixture obtained is applied to locks of gray hair containing 90% white hair. After 30 minutes of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried, to obtain the different shades.

The color of the locks was evaluated before and after exposure to light in the L * a * b * system, using a CM 2002 spectrophotometer.

MINOLTA ®, (Illuminant D65). In this system L * a * b *, L * represents the intensity of the color, a * indicates the axis of color green / red and b * the axis of color blue / yellow. The lower the value of L, the darker or more intense the color. The higher the value of a * the more the shade is red and the higher the value of b * the more the shade is blue.

The chromaticity of the color is calculated according to the following equation (ii):

C * = V (a *) ² + (b *) ²

In which a * and b * represent the values measured on locks of treated hair. The higher the value of C *, the greater the chromaticity of the color.

Table 1 - Power and chromaticity results obtained with the compound io (11) of the invention:

Compound (11) Λ / - hydrochloride [5 (4.5-diamino-1 / - / - Oxidation dyes - couplers / pyrazol-1 composition - yl) pentyllacetamide (10 ' ³ mole) | Β1ΒΙΙΒΜ1ΒΙΜΒΒΒΜΒ | ΒΒΒΙΒΜ | ΙΙΒ1 · ΙΜ ^ 2 - ({3 - [(2-hydroxyethyl) amino] -2-methylphenyl} amino) ethanol (10 ' ³ mole) / composition 1 24.8 16.79 Meta aminophenol (10 ' ³ mole) / composition 2 32.06 15.87 Resorcinol (10 ' ³ mole) / composition 3 37.15 11.85 2-methylresorcinol (10 ' ³ mole) / composition 4 34.66 15.12 6-hydroxybenzomorpholine (10 ' ³ mole) / composition 5 32.56 13.84 2-amino-3-hydroxypyridine (10 ' ³ mole) / composition 6 35.91 8.17 1H-indol-6-ol (10 ' ³ mole) / composition 7 34.89 13.66 5-amino-2-methylphenol (10 ' ³ mole) / composition 8 34.22 23.03 2-methyl-5-hydroxyethylaminophenol (10 ' ³ mole) / composition 9 37.21 21.59 2- (2,4-diaminophenoxy) ethanol hydrochloride (10 ' ³ mole) / composition 10 23.6 16.32 3-amino-2-chloro-6methylphenol hydrochloride (10 ' ³ mole) / composition 11 33.56 23.91 1-naphthol (10 ' ³ mole) / composition 13 29.49 18.48

2-amino-5-ethylphenol hydrochloride (10 ' ³ mole) / composition 14 26.63 19.13

Table 2 - Power and chromaticity results obtained with the compound (12) of the invention:

Oxidation dyes - couplers / composition Compound (12) 1- (5aminopentyl) -1 / - / pyrazole-4.5-diamine hydrochloride (10 ' ³ mole) L * VS* 2 - ({3 - [(2-hydroxyethyl) amino] -2-methylphenyl} amino) ethanol (10 ' ³ mole) / composition 15 19.69 16.65 Meta aminophenol (10 ' ³ mole) / composition 16 28.38 19.95 Resorcinol (10 ' ³ mole) / composition 17 32.98 13.43 2-methylresorcinol (10 ' ³ mole) / composition 18 32.57 17.23 6-hydroxybenzomorpholine (10 ' ³ mole) / composition 19 25.61 14.63 2-amino-3-hydroxypyridine (10 ' ³ mole) / composition 20 30.89 12.46 1 / - / - indol-6-ol (10 ' ³ mole) / composition 21 32.14 14.68 5-amino-2-methylphenol (10 ' ³ mole) / composition 22 31.74 24.76 2-methyl-5-hydroxyethylaminophenol (10 ' ³ mole) / composition 23 31.61 27.38 2- (2,4-diaminophenoxy) ethanol hydrochloride (10 ' ³ mole) / composition 24 21.5 14.82 3-amino-2-chloro-6methylphenol hydrochloride (10 ' ³ mole) / composition 25 25.86 29.8 1-naphthol (10 ' ³ mole) / composition 27 22.25 19.8 2-amino-5-ethylphenol hydrochloride (10 ' ³ mole) / composition 29 24.25 19.09

Table 3 - Power and chromaticity results obtained with the compound (10b) of the invention:

Oxidation dyes - couplers / composition

Compound (10b)

1- [5 (dimethylamino) penty l] -1 H-pyrazole4.5-diamine hydrochloride (10 ' ³ mole) L * VS* 2 - ({3 - [(2-hydroxyethyl) amino] -2-methylphenyl} amino) ethanol (10 ' ³ mole) / composition 30 22.59 16.31 Meta aminophenol (10 ' ³ mole) / composition 31 30.22 17.84 Resorcinol (10 ' ³ mole) / composition 32 33.95 12.61 2-methylresorcinol (10 ' ³ mole) / composition 33 32.42 15.63 6-hydroxybenzomorpholine (10 ' ³ mole) / composition 34 27.47 14.63 2-amino-3-hydroxypyridine (10 ' ³ mole) / composition 35 33.30 9.4 1 / - / - indol-6-ol (10 ' ³ mole) / composition 36 32.83 13.02 5-amino-2-methylphenol (10 ' ³ mole) / composition 37 28.11 25.03 2-methyl-5-hydroxyethylaminophenol (10 ' ³ mole) / composition 38 30.61 25.51 2- (2,4-diaminophenoxy) ethanol hydrochloride (10 ' ³ mole) / composition 39 19.36 16.16 3-amino-2-chloro-6methylphenol hydrochloride (10 ' ³ mole) / composition 40 28.97 29.6 1-naphthol (10 ' ³ mole) / composition 42 24.03 21.97 2-amino-5-ethylphenol hydrochloride (10 ' ³ mole) / composition 43 27.03 19.45

It appears that the compounds of the invention make it possible to obtain powerful and chromatic colors.

Comparative tests on chromaticity:

Chromaticity result

Compositions Chromaticity C * Compound according to the invention (11) N- [5- (4,5-diamino-1 H-pyrazol-1 -yl) pentyl] acetamide hydrochloride (10 ' ³ mole) + 1 H-indol-6-ol (10 ' ³ mole) Composition 7 13.66 Compound according to the invention (12) 14.68

1 - (5-aminopentyl) -1 H-pyrazole-4,5-diamine hydrochloride (10 ' ³ mole) + 1 H-indol-6-ol (10' ³ mole) Composition 21 Compound according to the invention (10b) 1 - [5- (dimethylamino) -pentyl] -1 H-pyrazole-4,5-diamine hydrochloride (10 ' ³ mole) + 1 H-indol-6-ol (10' ³ mole) Composition 36 13.02 Comparative compound 1-hexyl-1 H-pyrazole-4,5-diamine sulfate (10 ' ³ mole) + 1 H-indol-6-ol (10' ³ mole) Composition 44 8.97

It appears that the compounds of the invention make it possible to obtain significantly more chromatic colorations than that obtained with the comparative compound.

Claims (20)

1- Compound of formula (I) below: R H NOT \ R '2 H N-R. R. O) As well as its addition salts with organic or mineral acids, its tautomers, its solvates such as hydrates; Formula (I) in which: • R represents an atom or group chosen from: - hydrogen, - hydroxy, - ALK representing a group (C-i-C6) alkyl, or (C2-C6) alkenyl, linear or branched, preferably (C-i-C4) alkyl such as methyl; and - ALK-O- in which ALK is as defined above, preferably (C-i-C4) alkyl such as methyl; • Ri and R ₂ , identical or different, represent an atom or group chosen from: - hydrogen; - C1-C6 alkyl optionally substituted by one or more hydroxy radicals, preferably C1-C4 and more preferably C1-C2 such as methyl or hydroxymethyl; - (Ci-C6) (alkylthio) carbonyl, preferably (Ci-C2) alkylcarbonyl such as acetyl; or then Ri and R ₂ form, together with the nitrogen atom to which they are attached, a saturated or unsaturated heterocycle of 5 to 8 members, optionally substituted, or a heteroaryl comprising of 5 to 8 members, optionally substituted, this heterocycle or heteroaryl which may contain one or more additional heteroatoms chosen from the oxygen or nitrogen atom; and • R ₃ and R ₄ , identical or different, represent an atom or group chosen from: - hydrogen; and - (C-i-C6) alkyl (thio) carbonyl, preferably (C-i-C2) alkylcarbonyl such as acetyl. 2- Compound of formula (I) according to the preceding claim in which R represents an atom or group chosen from: - Hydrogen; - ALK representing a (C-i-C4) alkyl group; and - ALK-O- in which ALK is as defined above; particularly R represents a hydrogen atom or a (C-iC4) alkyl group, preferably R represents a hydrogen atom. 3- Compound of formula (I) according to claim 1 or 2 wherein ALK represents a group (CiC ₄ ) alkyl such as methyl, ethyl, n-propyl, tetrabutyl; preferably the compound or compounds of the invention are such that ALK represents a methyl group. 4- Compound of formula (I) according to any one of the preceding claims in which Ri and R ₂ , identical or different, represent an atom or group chosen from: - hydrogen; - C1-C4 optionally substituted by one or more hydroxy radicals, preferably Ci-C ₂ such as methyl or hydroxymethyl; and - (CiC ₄ ) alkylcarbonyl, preferably (CiC ₂ ) alkylcarbonyl such as acetyl. 5- Compound of formula (I) according to any one of the preceding claims in which R ₃ and R ₄ represent a hydrogen atom. 6- Compound of formula (I) according to any one of claims 1 to 4 in which Ri and R ₂ form together with the nitrogen atom to which they are attached a saturated heterocycle of 5 to 7 members, optionally substituted, or a heteroaryl comprising from 5 to 7 links, optionally substituted, this heterocycle or heteroaryl which may contain one or two additional heteroatoms chosen from the oxygen or nitrogen atom, preferably Ri and R ₂ together form with the nitrogen atom a group selected from imidazolyle pipéridino, pyrrolidino, pipérazino, morpholino optionally substituted by a group (Ci-C4) alkyl such as methyl. 7- Compound of formula (I) according to any one of the preceding claims wherein said compound of formula (I) is in salified form with n organic or mineral acids n HAn, with n =%; 1; 2; 3 or 4; preferably, the acid or acids are chosen from sulfonic acids such as methane sulfonic acid, paratoluene sulfonic acid, sulfuric acid, halogenated acids such as hydrochloric and hydrobromic acid, acids ( poly) (hydroxy) (C1-C6) alkylcarboxylic acids such as acetic acid, citric acid, or tartaric acid; more preferably, An represents a hemisulfate, sulfate, hydrochloride, acetate, methanesulfonate group; even more preferably hemisulfate, sulfate and hydrochloride; in particular, n HAn represents 0.5 H2SO4, 1 H2SO4, 2 H2SO4 2 HCl, 3 HCl, or 4 HCl. 8- Compound of formula (I) according to any one of the preceding claims chosen from the compounds of formula (! ’) Below: ι R ₂ η HAn (! ’) As well as their tautomers and their solvates such as hydrates; formula (I ’) in which: - R being as defined in any one of claims 1 to 3; 5 - R-ι and R ₂ being as defined in any one of the claims 1 and 4 to 6; - HAn represents an organic or mineral acid with An representing the anionic counterion of said organic or mineral acid; - n represents whole number or not, inclusive between 0.5 and 10 4, particularly n is 0.5; 1 or 2 ; it being understood that when n is greater than or equal to 2 then An can be identical or different between them; particularly n HAn is as defined in the preceding claim. 9- Compound of formula (I) or (I ’) according to any one of claims 1 to 5, 7 and 8 chosen from those of formula (I”) as well as its solvates such as hydrates: formula (I ”) in which - n represents an integer or not inclusive inclusive between 0.5 and 2, in particular n is 0.5, 1 or 2; - HAn is as defined in claim 7 or 8, particularly 5 An is an anionic counter ion chosen from sulfate, hydrochloride, tartrate, acetate, hydrobromide, tosylate, mesylate, methanesulfonate, citrate, more particularly, An is chosen from sulfate, hydrochloride, acetate, and methanesulfonate, preferentially An is chosen from sulfate, hydrochloride, and methanesulfonate, more preferably chosen from sulfate, and hydrochloride. 10- Compound of formula (I), (I ’) or (I”) according to any one of claims 7 to 9 in which n HAn represents 0.5 H2SO4, 1 H2SO4, 2 HCl. 11- Compound of formula (I), (I ') or (I ”) according to any one of the preceding claims chosen from the compounds of formula 1 to 32 below as well as their addition salts with organic or mineral acids, their tautomers , their solvates such as hydrates or solvates 20 of linear or branched alcohol such as ethanol or isopropanol: nh ₂ nh ₂ H ^Nx n ^ ^nh 2 0 ^N 'hTO ^NH 2 TO H 1: 1- (5-aminopentyl) -1 / - / - pyrazole-4,5- 2: / V- [5- (4,5-diamino-1 / - / - pyrazol- diamine 1 -yl) pentyl] acetamide 3: 1 - (5-aminopentyl) -3-methyl-1 Hpyrazole-4,5-diamine 4: A / - [5- (4,5-diamino-3-methyl-1 / - / pyrazol-1 -yl) pentyl] acetamide 5: 1- [5- (dimethylamino) pentyl] -1 / - / pyrazole-4,5-diamine 6: 1- [5- (dimethylamino) pentyl] -3methyl-1 / - / - pyrazole-4,5-diamine 7: 1 - [5- (diethylamino) pentyl] -1 Hpyrazole-4,5-diamine OH 8: 2.2 '- {[5- (4,5-diamino-1Hpyrazol-1-yl) pentyl] imino} diethanol OH 9: 1 - [5- (diethylam ino) pentyl] -3-methyl1 / - / - pyrazole-4,5-diamine 10: 2.2 '- {[5- (4,5-diamino-3methyl-1 H-pyrazol-1 yl) pentyl] imino} -diethanol / O NH, ^Νχ Ν ^ ^ΝΗ 2 / O NH,% ^ nh ₂ at/ H 11: 1- (5-aminopentyl) -3-methoxy-1 / - / pyrazole-4,5-diamine 12: / V- [5- (4,5-diamino-3-methoxy1 / - / - pyrazol-1 -yl) pentyl] acetamide / O NH,% ^ NH ₂ / O NH,% ^ NH ₂ 13: 1- [5- (dimethylamino) pentyl] -3methoxy-1 / - / - pyrazole-4,5-diamine 14: 1- [5- (diethylamino) pentyl] -3methoxy-1 / - / - pyrazole-4,5-diamine / O NH,% ^ nh ₂ nh ₂ % © νη ₂ hcl fi J (J r OH 15: 2.2 '- {[5- (4,5-diamino-3-methoxy-1 / - / pyrazol-1-yl) pentyl] imino} -diethanol 16: 1- [5- (pyrrolidin-1-yl) pentyl] 1 H-pyrazole-4,5-diamine 17: 1 - [5- (morpholin-4-yl) pentyl] -1 Hpyrazole-4,5-diamine 18: 1 - [5- (piperazin-1 -yl) pentyl] 1 / - / - pyrazole-4,5-diamine 19: 1 - [5- (piperidin-1 -yl) pentyl] -1 Hpyrazole-4,5-diamine 20: 3-methyl-1 - [5- (pyrrolidin-1 yl) pentyl] -1 / - / - pyrazole-4,5-diamine 21: 3-methyl-1- [5- (morpholin-4- 22: 3-methyl-1- [5- (piperazin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine yl) pentyl ] -1 / - / - pyrazole-4,5-diamine 1 / - / - pyrazole-4,5-diamine methylpiperazin-1 -y l) penty l] -1 Hpyrazole-4,5-diamine / o nh ₂ % ^ nh ₂ / O NH, ⁿ ^ nh ₂ ct 25: 3-methoxy-1- [5- (pyrrolidin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine 26: 3-methoxy-1- [5- (morpholin-4yl) pentyl] -1 / - / - pyrazole-4,5-diamine —0 NH, ^ν 'Λνη ₂ / O NH, ^N ^ NH ₂ H ₃ c ^{/ N} ^ 27: 3-methoxy -1- [5- (4-methylpiperazin1 -y l) penty l] -1 / - / - pyrazole-4,5-diamine 28: 3-methoxy-1- [5- (piperazin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine —O NH, ^N ' _n ^ nh ₂ NH, ^N 'N ^K NH ₂ Cf 29: 3-methoxy-1- [5- (piperidin-1yl) pentyl] -1 / - / - pyrazole-4,5-diamine 30: 1 - [5- (1 / - / - imidazol-1 -yl) pentyl] 1 / - / - pyrazole-4,5-diamine \ NH ₂ % ^ nh ₂ / ^{0 NH} 2 V 31: 1- (5- (1/7-imidazol-1-yl) pentyl] -3- 32: 1 - (5- (1 H-imidazol-1 -yl) pentyl] - 1-methyl-H-pyrazole-4,5-diamine 3-methoxy-1 H-pyrazole-4,5diamine 12- Process for preparing the compounds of structure (I), (Γ) or (I ”) as defined in any one of the preceding claims according to scheme 1 or 2 below: 5 Diagram 1: Compounds 4 to 11 in which R is as defined in any one of claims 1 to 3 in formula (I), T represents a (hetero) aryl group such as phenyl, Ra, Rb and R _c , identical or different, 5 represent a (Ci-C _e ) alkyl group such as methyl, boc represents a group protecting the amine function, in particular the (CiC ₆ ) alkylcarbamates such as ter-butylcarbamate; and X represents an oxygen or sulfur atom, preferably oxygen An and n are as defined in any one of claims 7 to 10, x is 1 or 2, and Z represents an optionally substituted (hetero) aryl group such as phenyl; Process which consists in reacting: - a derivative 4 with a nitrile derivative R-CH = CH-CN with hydrazine to conduct after a nucleophilic reaction of hydrazine on 4 of Michael 1,2 type then addition of the compound R-CH = CH-CN, preferably at low temperature such as 0 ° C and under an inert atmosphere, to yield the compound of formula 5; then a compound 5 with an alkaline agent, preferably sterically hindered, in particular chosen from (C ₃ -Ci ₀ ) alkanolate of alkaline and alkaline earth salt, the alkyl part of which is branched or sterically hindered, such as the alkali metal terbutylates, alkaline earth or ammonium preferably sodium or potassium, preferably under an inert atmosphere in an organic solvent preferably polar protic such as (C ₃ -Cio) alkanol whose alkyl part is linear or branched, such as terbutanol to conduct after intramolecular cyclization to the 5aminopyrazole 6 derivative; - Compound 6 which is nitrated or nitrosed in particular in a practical polar solvent such as ethanol and at low temperature such as at 0 ° C by the addition of (C ^ Cejalkylnitrile, such as isopentyl nitrile, followed by the addition of mineral acid, preferably halogenated such as hydrochloric acid, at low temperature preferably at 0 ° G, then ammonia is added, in particular at a pH above 11, optionally followed by preferably water extraction! halogenethane such as dichloromethane, possibly followed by filtration to yield the nitro compound (so) 7; or then compound 6 which reacts with a diazonium salt ZN ~ N ⁺ Q with Q 'representing a counter ion anionic, and Z representing an optionally substituted aryl or heteroaryl group such as phenyl optionally substituted by a halogen, a (Ci-C ₄ ) alkyl group, an SO ₃ R 'group with R' representing a hydrogen atom or an alkali metal , alkaline earth such as sodium; in particular in a solvent such as water, an alcohol and at a temperature between -5 ° C and 10 ° C, and once the azo coupling reaction is complete (reaction followed by TLC), to lead to the azo compound 7 'preferably in a medium at neutral and precipitated pH, the solid can be purified by filtration; if, however, the yield turns out to be low due to the solubility of the azo, if this can be extracted with a polar aprotic organic solvent of the ethyl acetate type or a halogenated solvent, preferably chlorinated, such as dichloromethane and compound 7 'is isolated after evaporation of the solvent; compounds 7 or 7 ’with a reducing agent such as with a catalyst such 10 that Ni or Pd in the presence of hydrogen or hydrazine preferably under an inert atmosphere in particular in a polar protic solvent such as ethanol to yield the compounds 8, and 9 belonging to the compound of formula (I) as defined previously; said compound may optionally; 15 - be salified using organic or mineral acid, as defined above, preferably using in particular sulfuric mineral acid such as sulfuric acid to yield compound 11 belonging to the compound of formula ( I) as defined above - be (thio) acetylated using (thio) ester or (thio) acid R _a -C (X) -X-R ', 20 Rb-C (X) ~ X-R ', and Rc-C (X) -X-R' with R 'representing a hydrogen atom or a (Cj-C ₆ ) alkyl group to yield compound 10 or 12, compound 12 belonging to the compound of formula (I) as defined in one of claims 1 to 11; Diagram 2: Compounds 4 'to 10' in which R is as defined above in formula (I), T, R _a , boc, X, x, Z, R _a , Rb, Rc, An and n are as defined above and R \, R'2, identical or different, represent a group 5 ₀ CiC alkyl optionally substituted by one or more hydroxy radicals; Process which consists in reacting: - a 4 ’derivative with a nitrile derivative R-CH = CH-CN with hydrazine to conduct after a nucleophilic reaction of hydrazine on 4’ of the 10 Michael 1,2 followed by addition of the compound R-CH = CH-CN, preferably at low temperature such as Û ° C and under an inert atmosphere, to yield the compound of formula 5 ’; then - a 5 ′ compound with an alkaline agent, preferably sterically hindered, in particular chosen from (Cs-Ciolâlcanolâte de sel Alkaline and alkaline earth in which the alkyl part is branched or sterically hindered, such as the alkali metal, alkaline earth or ammonium terbutylates preferably of sodium or potassium, preferably under inert atmosphere in an organic solvent preferably polar protic such that (C3-C ₁₀ ) alkanol whose alkyl part is linear or branched, such as terbutanol to lead after intramolecular cyclization to the derivative of 5aminopyrazole type 6 '; 5 - compound 6 'which is nitrated or nitrosed in particular in a practical polar solvent such as ethanol and at low temperature such as at 0 ^a C by the addition of (Ci-C ₆ ) alkylnitrile, such as isopentyl nitrile, followed by the addition of mineral acid, preferably halogenated such as hydrochloric acid, at low temperature preferably at 0 ° G, then is 10 added ammonia, especially at a pH above 11, possibly followed by extraction, preferably water! halogenethane such as dichloromethane, optionally followed by filtration to yield the 7 ”nitro (so) compound; or the compound 6 'which reacts with a diazonium salt ZN = N ⁺ Q' with Q ' 15 and Z as defined above in particular in a solvent such as water, an alcohol and at a temperature between -5 ° C. and 10 ° C., and once the azo coupling reaction is complete, (reaction followed by TLC), to lead to the 7 ”azo compound preferably in a medium at neutral pH and precipitates, the solid can be purified by filtration; If, however, the yield is found to be low due to the solubility of the azo, this can be extracted with a polar aprotic organic solvent of ethyl acetate type or a halogenated solvent, preferably chlorinated, such as dichloromethane and compound 7 ”'Is isolated after evaporation of the solvent; The compounds 7 ”or 7” which can react with a reducing agent such as with a catalyst such as Ni or Pd in the presence of hydrogen or hydrazine preferably under an inert atmosphere in particular in a practical polar solvent such as ethanol to yield the compounds 8 ′ belonging to the compound of formula (I) as defined in a Any of claims 1 to 11; said compound 8 'can optionally; - be salified using organic or mineral acid, as defined above, preferably using in particular sulfuric mineral acid such as sulfuric acid to yield the compound 10 ′ belonging to the compound of formula ( I) as defined in any one of claims 1 to 11; - be (thio) acetylated using (thio) ester or (thio) acid R _a -C (X) -X-R ', Rb-C (X) -X-R', and R _c - C (X) -XR 'with R' representing an atom 5 of hydrogen or a (Ci-C6) alkyl group to yield compound 9 'belonging to the compounds of formula (I) as defined as defined in any one of Claims 1 to 11. 13- Compound chosen from 6, 6 ', 7, 7', 7 ”, 7” \ 8, and 9 'as defined in io the preceding claim as well as their acid or base salts, organic or mineral, their optical, geometric isomers, tautomers, and their solvates such as hydrates. 14- Cosmetic composition, which comprises i) one or more components (s) of formula (I), (Γ), or (I ”) as defined in any one of claims 1 to 11. 15- Composition according to the preceding claim which comprises ii) one or more additional oxidation base (s) chosen from 20 para-phenylenediamines, bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols and heretocyclic bases different from the compound (s) of formula (I), (! '), Or (I ”) as defined in claims 1 to 11. 25 16- Composition according to any one of claims 14 or 15 which comprises iii) one or more coupling agents in particular chosen from meta-phenylenediamines, meta-aminophenols, metadiphenols, coupling agents based naphthalene and heterocyclic coupling agents as well as the corresponding addition salts, 30 particularly chosen from the Compounds of formula (II) and (II ’): As well as their acid or base salts, organic or mineral, and their solvates such as hydrates; Formulas (11) and (II ’), in which: - X-ι, and X ₂ , identical or different, represent a group chosen from hydroxy, (di) (Ci-eXalkyl) amino, (di) hydroxy (CiC ₆ ) alkylamino; - Y represents a hydrogen atom, (Ci-C6) (hydroxy) a) kyle, or then two adjacent substituents Y and Xi and / or Y and X ₂ form together with the carbon atoms which carry them A heterocycle group possibly substituted, such as morpholinyl, piperazinyl, piperidinyl preferably a hydrogen atom, (Ci-C ₆ ) alkyl, or then two adjacent substituents Y and X-ι together form with the carbon atoms which carry them an optionally substituted morpholinyl group by a group (CrC ^ alkyl; - p is 1, 2, 3 or 4; - t is 1, 2 or 3; It being understood that when p or t is greater than or equal to 2 the groups Y are identical or different from each other. 17-Composition according to any one of claims 14 to 16 which comprises iii) one or more coupling agent (s) chosen from the compounds of formula (ll _a ) and (ll ' _a ): As well as their aid or base salts, organic or mineral, and their solvates such as hydrates; Formulas (lla) and (ll’a) in which: - Xi and X ₂ are as defined in the preceding claim, preferably Xi and / or X ₂ represents (s) a hydroxy, amino, or (hydroxy) aikylamino group; - Y ·) represents a hydrogen atom or a group (Cq-C6alkyl; 5 - Y ₂ represents a hydrogen atom, or forms with the substituent Y ₂ an optionally substituted heterocycle, such as morpholinyl, piperazinyl, piperidinyl preferably morpholinyl optionally substituted by a (Ci-C ₄ ) alkyl group; preferably the coupler (s) is (are) chosen from: 2o methylresorcinol, 6-hydroxy benzomorpholine; 2-amino-3 ~ hydroxypyridine · 2 ({3 - [(2-hydroxyethyl) aminoi-2-methylphenyl} amino) ethanol as well as their acid or base salts and their solvates such as hydrates. 18- Process for coloring keratin fibers and in particular 15 human keratin fibers such as the hair using a dye composition as defined above in any one of claims 14 to 17. 19- Method according to the preceding claim, characterized in that zo the color is revealed at acidic, neutral or alkaline pH using at least one oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately; preferentially the oxidizing agent (s) is (are) chosen from hydrogen peroxide, 25 urea peroxide, alkali metal bramates, persalts such as perborates and persulfates, peracids and oxidase enzymes. 20- Use of one or more compound (s) of formula (I), (P) or (I ”) as defined in any of claims 1 to 11, optionally 30 in the presence of additional oxidation base (s) as defined in claim 15, and optionally in the presence of one or more couplers) as defined in any of claims 16 or 17, and optionally in the presence of oxidizing agent (s) in particular as defined in claim 19, for dyeing keratin fibers, in particular human fibers such as the hair. 21-Device with several compartments, or dye kit with several compartments, a first compartment of which contains a dye composition as defined in any one of claims 14 to 17 and a second compartment of which contains an oxidizing composition in particular as defined in claim 19.