FR2886140A1 - Composition useful for coloring of keratinous fibers comprises an oxidation base such as diamino-N,N-dihydropyrazolone derivatives or their salts and a coupling agent i.e. an indoline or an indole derivative - Google Patents

Abstract

Composition for coloring of keratinous fibers comprises an oxidation base such as diamino-N,N-dihydropyrazolone derivatives (I) or their salts and a coupling agent i.e. an indoline derivative (II) or an indole derivative (III) or their addition salts, in a medium. Composition for coloring of keratinous fibers comprises an oxidation base such as diamino-N,N-dihydropyrazolone derivatives of formula (I) or their salts and a coupling agent i.e. an indoline derivative of formula (II) or an indole derivative of formula (III) or their addition salts, in a medium. Either R1, R2Q; Q : 1-10C alkyl (optionally substituted by OR5, NR6R7, carboxy, sulfonic, CONR6R7, SO2NR6R7, heteroaryl or T), T or 5-6 membered heteroaryl (optionally substituted by 1-4C alkyl or 1-2C alkoxy); or NR1R25-7 membered heterocycle (optionally substituted by halo, amino, (di)1-4C alkyl amino, OH, COOH, carboxamido, 1-2C alkoxy or 1-4C alkyl (optionally substituted by OH, amino, (di)alkylamino, alkoxy, carboxy or sulfonyl)); either R3, R4H or Q; or NR3R4, NR1R25-7 membered heterocycle (where the carbons are optionally replaced by O or N and optionally substituted); T : aryl (optionally substituted by 1-4C alkyl, OH, 1-2C alkoxy or (di)1-4C alkyl amino); R5H, 1-4C alkyl (optionally substituted by 1-2C alkoxy, OH, CONR8R9, SO2R8 or T) or T; R6, R7R5, CONR8R9 or SO2R8; R8, R9H, 1-4C alkyl (optionally substituted by OH or 1-2C alkoxy); R1aH or ((poly)hydroxy) 1-10C alkyl; R2aH, carboxy, 1-10C alkyl or 1-10C alkoxy carbonyl; R3aH or 1-10C alkyl; and R4a, R5aH, 1-10C alkyl or 1-10C alkyl carbonyl. Independent claims are included for: (1) dyeing of keratinous fibers comprising application of the composition on fibers in the presence of an oxidizing agent; and (2) a device with several compartments comprising the composition and the oxidizing agent in different compartments. [Image].

Description

COMPOSITION FOR DYING KERATIN FIBERS

  The subject of the invention is a composition for dyeing keratinous fibers, and in particular human keratinous fibers, such as the dermal fibers, such as dyestuffs, hair, comprising at least one diamino-N, N-dihydropyrazolone type oxidation base or one of its addition salts and at least one indole or indoline type coupler or one of its addition salts, and the method coloration using such a composition.

  It is known to dye keratinous fibers, and in particular human keratinous fibers such as the hair, with dyeing compositions comprising oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, compounds heterocyclic such as diaminopyrazole derivatives, pyrazolo [1,5-a] pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives, indole derivatives, indoline derivatives generally referred to as oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored or coloring compounds. This produces permanent colorations.

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

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

  The use of oxidation bases such as para-phenylenediamine and para-aminophenol derivatives makes it possible to obtain a fairly broad range of colors at basic pH without, however, achieving good chromaticity shades while conferring on the hair excellent properties of intensity of color, variety of shades, uniformity of color and tenacity to external agents.

  The use of these bases at neutral pH does not allow to reach a range of varied shades, in particular for hot shades such as reds and oranges.

  The object of the present invention is to provide novel compositions for dyeing keratinous fibers which make it possible to obtain a coloring of various shades, in particular natural, powerful, chromatic, aesthetic, not very selective and resistant to the various aggressions which the hair such as shampoos, light, sweat and permanent deformities.

  The subject of the present invention is therefore a dyeing composition for keratinous fibers comprising, in a suitable medium: E at least one oxidation base chosen from a derivative of diamino-N, Ndihydropyrazolone of formula (I) or one from its addition salts:

O NH / 2

  In which: R 1, R 2, R 3 and R 4, which may be identical or different, represent: a C 1 -C 10, preferably C 1 -C 6, linear or branched alkyl radical optionally substituted with one or more radicals chosen from the group consisting of an ORS radical, a NR6R7 radical, a carboxy radical, a sulphonic radical, a carboxamido radical CONR6R7, a sulphonamido radical SO2NR6R7, a heteroaryl, an aryl optionally substituted with one or more (C 1 -C 4) groups alkyl, hydroxy, (C 1 -C 2) alkoxy, amino, (di) (C 1 -C 2) alkylamino; an aryl radical optionally substituted by one or more (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino or (di) C 1 -C 2 alkylamino radicals; a 5- or 6-membered heteroaryl radical, optionally substituted with one or more radicals chosen from a (C 1 -C 4) alkyl or (C 1 -C 2) alkoxy radical; R3 and R4 may also represent a hydrogen atom; R6, R6 and R7, which may be identical or different, represent: a hydrogen atom; a linear or branched C 1 -C 4 alkyl radical optionally substituted with one or more radicals chosen from a hydroxyl, C 1 -C 2 alkoxy, carboxamido CONR 8 R 9, sulfonyl SO 2 R 8 radical, optionally substituted with a (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; aryl optionally substituted with a (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; R6 and R7, which may be identical or different, may also represent a carboxamido radical CONR8R9; a sulphonyl radical SO2R8; R8 and R9, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C2 alkoxy radicals; R 1 and R 2, on the one hand, and R 3 and R 4, on the other hand, can form, with the nitrogen atom or atoms to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle, optionally substituted by one or more radicals selected from the group consisting of halogen atoms, amino, (di) (C 1 -C 4) alkylamino, hydroxy, carboxy, carboxamido, (C 1 -C 2) alkoxy radicals, C 1 -C 4 alkyl radicals; optionally substituted with one or more hydroxy, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals; R3 and R4 may also form together with the nitrogen atom to which they are attached a 5- or 7-membered heterocycle whose carbon atoms may be replaced by an optionally substituted oxygen or nitrogen atom; and E at least one coupler chosen from an indoline derivative of formula (II), an indole derivative of formula (III), and one of their addition salts: R ', r R, 50 R' in which: R 'represents a hydrogen atom; a linear or branched C 1 -C 4, preferably C 1 -C 6, alkyl radical; a C, -C, o, preferably C1-C6, linear or branched (poly) hydroxyalkyl radical; R'2 represents a hydrogen atom; a carboxyl radical; a linear or branched C 1 -C 4, preferably C 1 -C 6, alkyl radical; a C 1 -C 10, preferably C 1 -C 6, linear or branched alkoxycarbonyl radical; R'3 represents a hydrogen atom; a linear or branched C 1 -C 10, preferably C 1 -C 6, alkyl radical; R'4 and R'5 represent, independently of one another, a hydrogen atom; a linear or branched C 1 -C 10, preferably C 1 -C 6, alkyl radical; an alkylcarbonyl radical C, -C, o, preferably C1-C6, linear or branched.

  The present invention makes it possible in particular to obtain a coloring of the keratinous fibers with varied shades, powerful, aesthetic, not very selective and resistant to the various attacks that can undergo the hair such as shampoos, light, sweat and permanent deformations. It allows in particular to obtain natural nuances. It also allows to obtain intense and varied colorations at neutral pH.

  Another subject of the invention is a process for dyeing keratin fibers using the composition of the present invention, as well as the use of this composition for dyeing keratinous fibers.

  Finally, the subject of the invention is a dyeing kit comprising on the one hand a dyeing composition containing an oxidation base of formula (I) and a coupler of formula (II) and / or a coupler of formula (III) and on the other hand a composition containing an oxidizing agent.

  In the context of the invention, the term "alkyl radical" is understood to mean linear or branched C 1 -C 6 alkyl radicals, unless otherwise indicated, preferably C 1 -C 6, even more preferentially C 1 -C 4, such as the methyl radical, ethyl, propyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl.

  A (poly) hydroxyalkyl radical is a mono or polysubstituted alkyl with a hydroxyl radical, ie an alkyl radical which may be substituted by one or more hydroxyl radicals.

  More particularly, in formula (I), the radicals R 1 and R 2, which are identical or different, are chosen from: a C 1 -C 6 alkyl radical optionally substituted by a hydroxyl radical, (C 1 -C 2) alkoxy, amino, (di ) alkyl (C, -C2) alkylamino; a phenyl, methoxyphenyl, ethoxyphenyl or benzyl radical.

  Preferably, the radicals R 1 and R 2, which may be identical or different, are chosen from a methyl, ethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl and phenyl radical.

  According to another embodiment, the radicals R 1 and R 2 together with the nitrogen atoms to which they are attached form a 5- or 6-membered ring, saturated or unsaturated, optionally substituted.

  Preferably, the radicals R 1 and R 2 together with the nitrogen atoms to which they are attached form a pyrazolidine pyridazolidine ring, optionally substituted with one or more C 1 -C 4 alkyl, hydroxy, (C 1 -C 2) alkoxy radicals, carboxy, carboxamido, amino, (di) (C 1 -C 2) alkylamino.

  Even more advantageously, the radicals R 1 and R 2 together with the nitrogen atoms to which they are attached form a pyrazolidine, pyridazolidine ring.

  As regards the radicals R3 and R4, the latter, which are identical or different, are more particularly chosen from a hydrogen atom; a linear or branched C1-C6 alkyl radical, optionally substituted by one or more hydroxyl, (C1-C2) alkoxy, amino, (di) alkyl (C1 C2) amino radicals; a phenyl radical optionally substituted by one or more hydroxyl, amino, (C 1 -C 2) alkoxy radicals.

  Preferably, the radicals R3 and R4, which may be identical or different, are chosen from a hydrogen atom, a methyl, ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl or 2-carboxyethyl radical. According to a particular embodiment, the radicals R 3 and R 4 represent a hydrogen atom.

  According to another embodiment, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached form a 5- or 7-membered ring chosen from the heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine; said rings may be substituted by one or more hydroxy, amino, (di) (C 1 -C 2) alkylamino, carboxy, carboxamido, C 1 -C 4 alkyl radical optionally substituted by one or more hydroxy, amino, (di) alkylamino radicals; in C1-C2.

  More particularly, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached form a 5- or 7-membered ring chosen from pyrrolidine, 2,5-dimethylpyrrolidine and pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine 2- (diethylcarboxamido) pyrrolidine, 2-hydroxymethyl pyrrolidine, 3,4-dihydroxy-2-hydroxymethyl pyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxy pyrrolidine, 3-amino pyrrolidine, 3-methylamino pyrrolidine, 3dimethylamino-pyrrolidine, 4-amino-3-hydroxy-pyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) -amino-pyrrolidine, piperidine, 2,6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperidine, 2- hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine, 3hydroxypiped ridine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxyhomopiperidine, 2-carboxamido-homopiperidine, homopiperazine, N-methyl-homopiperazine, N- (2-hydroxyethyl) -homopiperazine.

  Preferably, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached form a 5- or 7-membered ring chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3dimethylamino-pyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, piperidine, hydroxypiperidine, homopiperidine, diazepane, N-methyl homopiperazine, N-3-hydroxyethylhomopiperazine.

  According to an even more preferred embodiment of the invention, the radicals R 3 and R 4 together with the nitrogen atom to which they are attached form a 5-membered ring such as pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, 3-dimethylaminopyrrolidine.

  The compounds of formula (I) may optionally be salified with strong mineral acids such as, for example, HCl, HBr, HI, H 2 SO 4, H 3 PO 4, or organic acids such as, for example, acetic, lactic, tartaric or citric acid. or succinic, benzenesulfonic, para-toluenesulfonic, formic, methanesulfonic.

  They may also be in the form of solvates, for example a hydrate or a linear or branched alcohol solvate such as ethanol or isopropanol.

  By way of examples of derivatives of formula (I), mention may be made of the compounds presented below or their addition salts: 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3 -one; 4-amino-5-methylamino-1,2-dimethyl-1,2-dihydropyrazol-3-one; 4-amino-5-dimethylamino-1,2-dimethyl-1,2-dihydro-pyrazol-3one; 4-amino-5- (2-hydroxyethyl) amino-1,2-dimethyl-1,2-dihydro-pyrazol-3one; 4-amino-5- (pyrrolidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4-amino-5- (piperidin-1-yl) -1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4,5diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5méthylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5diméthylamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino5- (2-hydroxyethyl) amino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (pyrrolidin-1-yl) -1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 4-amino-5- (piperidin-1-yl) -1,2-di- (2-hydroxyethyl) -1,2-dihydropyrazol-3-one; 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4,5diamino-1,2-phenyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1-ethyl-2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-2-ethyl-1-methyl-1,2dihydro-pyrazol-3-one; 4,5-diamino-1-phenyl-2-methyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-2-phenyl-1-methyl-1,2-dihydro-pyrazol-3-one; 4,5diamino-1- (2-hydroxyethyl) -2-methyl-1,2-dihydro-pyrazol-3-one; 4,5diamino-2- (2-hydroxyethyl) -1-methyl-1,2-dihydro-pyrazol-3-one; 2,3-diamino-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-methylamino-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3dimethylamino-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-ethylamino-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-isopropylamino-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3 (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3- (2-hydroxypropyl) amino-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-bis (2-hydroxyethyl) amino-6,7-dihydro-1H, SH-pyrazolo [1,2a] pyrazol-1-one; 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, SHpyrazolo [1,2-a] pyrazol-1-one; 2-amino-3- (3-hydroxy-pyrrolidin-1-yl) -6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3- (piperidin-1-yl) -6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-6hydroxy-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-6-methyl-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-6-dimethyl-6,7-dihydro-1H, SH-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-5,6,8,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one; 2,3-diamino-5,8-dihydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one; 4-Amino-5-dimethylamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-ethylamino-1,2dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-isopropylamino-1,2-dihydropyrazol-3-one; 4-Amino-1,2-diethyl-5- (2-hydroxy-ethylamino) -1,2-dihydropyrazol-3-one; 4-Amino-5- (2-dimethylamino-ethylamino) -1,2-diethyl-1,2dihydro-pyrazol-3-one; 4-Amino-5- [bis- (2-hydroxy-ethyl) -amino] -1,2diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (3-imidazol-1-propylamino) -1,2-dihydro-pyrazol-3-one; 4-Amino-5-dimethylamino-1,2diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-ethylamino-1,2dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5-isopropylamino-1,2-dihydropyrazol-3-one; 4-Amino-1,2-diethyl-5- (2-hydroxy-ethylamino) -1,2-dihydropyrazol-3-one; 4-Amino-5- (2-dimethylamino-ethylamino) -1,2-diethyl-1,2dihydro-pyrazol-3-one; 4-Amino-5- [bis- (2-hydroxy-ethyl) -amino] -1,2diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (3-imidazol-1-propylamino) -1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5- (3-hydroxypyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one; 4-Amino-1,2-diethyl-5pyrrolidin-1-yl-1,2-dihydro-pyrazol-3-one; 4-Amino-5- (3-dimethylaminopyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 4-Amino-1,2diethyl-5- (4-methyl-piperazin-1-yl) -pyrazolidin-3-one; 2,3-Diamino-6hydroxy-6,7-dihydro-5H-pyrazolo [1,2-a] pyrazol-1-one; some of which are shown below to illustrate the names by chemical structures: O, CNH2 4,5-Diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one

H C s N 2 CH3

  NHZ 4,5-Diamino-1,2-diethyl-1,2-dihydro C 2 H 5 NO, -pyrazol-3-one

N NHZ c2H5

  O, NHZ 4,5-Diamino-1,2-diphenyl-1,2-dihydro-pyrazol-3-one PhNN NH 2 Ph 2 NH 4 4,5-Diamino-1-ethyl-2-methyl-1,2-dihydro-pyrazol-3-one 1-Dihydro-pyrazol-3-H3CN NH2 one C2H5 O, CNH2 4,5-Diamino-1-phenyl-2-methyl-1,2-dihydro-pyrazol-H3c-N2-one Ph 0, NH2 C2H5 N 4-Amino-5- (pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-1-pyrazol-3-one C 2 H 5 O, NH 2 4-Amino-5- (3-dimethylaminopyrrolidin-1-yl) 1,2,3-Dihydro-pyrazol-3-one-1,2-dihydro-pyrazol-3-one-C2H5-NN N-CH3 C2H5 O, NH2 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-dihydro-pyrazol-3-one] N-pyrazol-1-one-NH 2 O, NH 2 -Amino-3-methylamino-6,7-dihydro-1H, 5H-N-pyrazolo [1,2-a] pyrazol-1-one N, H, NO, NH 2 2-Amino-3-ethylamino-6,7-dihydro-1H, 5H-N-pyrazolo [1,2-a] pyrazol-1-one,

O NHZ

  NH 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2a] pyrazol-1-one

OH

  O, NH 2 NH 2-amino-3- (2-hydroxypropyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one

OH

  O, NH 2 2-amino-3-bis (2-hydroxyethyl) amino-6,7-dihydro-N 1 H, 5H-pyrazolo [1,2-a] pyrazol-1-one

N N C /

OH

  O NH 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-, pyrazolo [1,2-a] pyrazol-1-one N, NC / O NH 2 2 -amino-3- ( pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-N-pyrazolo [1,2-a] pyrazol-1-one, O, NH 2 -amino-3- (3-hydroxypyrrolidin-1) -yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one N

OH

NOT

O NHZ N, NFi2

  N-2,3-diamino-6-hydroxy-6,7-dihydro-1H, SH-HO pyrazolo [1,2-a] pyrazol-1-one O NH 2 2,3-diamino-6-methyl-6 7-dihydro-1H, SH-N NH 2 pyrazolo [1,2-a] pyrazol-1-one O, NH 2 2,3-diamino-6,6-dimethyl-6,7-dihydro-1H, SH N-pyrazolo [1,2-a] pyrazol-1-one NH 2 -NH 2 N 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-N-NH 2 pyridazino [1,2] 1α, 2α-2,3-diamino-5,8-dihydro-1H, 6H-pyridazino [1,2-O] NH 2 α] pyrazol-1-one O, CNH 2 4,5-diamino-1-one 1- (2hydroxyethyl) -2-methyl-1,2-H-CN (NH-dihydro-pyrazol-3-one) N 2

OH

  O NH 2 4,5-diamino-2- (2-hydroxyethyl) -1-methyl-1,2-N NH 2 dihydro-pyrazol-3-one. i

  Among these compounds, the diamino-N, N-dihydropyrazolone derivatives of formula (I) or their particularly preferred addition salts are the following: 2,3-Diamino-6,7-dihydro-1H, 5H- pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2diéthyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one 4-amino-1,2-diethyl-5-pyrrolidin-1-yl-1, 2-dihydro-pyrazol-3-one; 4-Amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2diethyl-1,2-dihydro-pyrazol-3-one; 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one.

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

  According to a particular embodiment of the invention, R 'is chosen from a hydrogen atom; an alkyl radical. For example, R 'may be a hydrogen atom; a methyl radical; an ethyl radical; a propyl radical; a butyl radical.

  According to a particular embodiment of the invention, R'2 is a hydrogen atom or a carboxyl radical.

  According to a particular embodiment of the invention, R'3 is a hydrogen atom.

  According to a particular embodiment of the invention, R'4 is a hydrogen atom.

  According to a particular embodiment of the invention, R'5 is a hydrogen atom.

  In general, the addition salts of the compounds of formulas (II) and (III) which can be used in the context of the invention are especially chosen from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

  As examples of indoline derivatives of formula (II), mention may be made of 5,6-dihydroxyindoline; N-methyl-5,6-dihydroxyindoline; N-methyl-5,6-dihydroxyindoline; N-propyl-5,6-dihydroxyindoline; N-butyl-5,6-dihydroxyindoline; 5,6-dihydroxyindoline-2-carboxylic acid. Among these compounds, the particularly preferred indoline derivatives of formula (II) are 5,6-dihydroxyindoline; 5,6-dihydroxyindoline-2-carboxylic acid.

  As examples of indole derivatives of formula (III), mention may be made of 5,6-dihydroxyindole; N-methyl-5,6-dihydroxyindole; N-ethyl-5,6-dihydroxyindole; Dihydroxyindole; 2,3-dimethyl-5,6-dihydroxyindole; 2-ethoxycarbonyl-5,6-dihydroxyindole. Among these compounds, 5,6-dihydroxyindole is particularly preferred.

  In the composition of the present invention, the coupler (s) of formula (II) or (III) are in general each present in an amount of between 0.001 and 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.

  The dye composition of the invention may contain other oxidation bases and other couplers different from those useful in the present invention and conventionally used for dyeing keratinous fibers.

  The composition of the present invention may for example comprise additional oxidation bases selected from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, orthophenylenediamines, heterocyclic bases other than derivatives thereof. of formula (I) as defined above and their addition salts.

  Among the para-phenylenediamines, there may be mentioned, for example, para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-dipropyl para-phenylenediamine, 4-amino N, N-diethyl-3-methylaniline, N, N-bis- (3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (13- hydroxyethyl) amino 2-methylaniline, 4-N, N-bis- (13-hydroxyethyl) amino 2-chloroaniline, 2-13-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl paraphenylenediamine, N- (13-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, [3-hydroxyethyl) para- phenylenediamine, N - ((3'-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenylparandyl Npropyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydrox yindole, 5,6-dihydroxyindole-2-carboxylic acid; 2-methyl-5,6-dihydroxyindole; 3-methyl-5,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-phenylenediamine, 2- 13-hydroxyethyloxy para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N- (13-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

  Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl paraphenylenediamine, 2-13-hydroxyethyl para-phenylenediamine, 2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (13-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy paraphenylenediamine, and their addition salts with an acid are particularly preferred.

  Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( 13-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid.

  Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplified. methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (13-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid.

  Examples of ortho-aminophenols include 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 2-amino phenol acetamido, and their salts. addition with an acid.

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

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

  Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described, for example, in the patent application FR 2 801. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-ylpyrazolo [1,5-a] pyridin-3-ylamine; 3-aminopyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine, pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine 15; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-aminopyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydoxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition with an acid or with a base.

  Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 23 59 399; JP 88-169571; JP 05-63124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2 , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-trinaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2,750,048 and among which mention may be made of pyrazolo [1, 5-a] pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [1], 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2, 6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N-7,7-tetramethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their acid addition salts and their tautomeric forms, when tautomeric equilibrium exists.

  Among the pyrazole derivatives, mention may be made of the compounds described in DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino-methyl pyrazole, 4,5-diamino-1- (3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethylhydrazino-pyrazole, benzyl 4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-methyl-pyrazole, 4,5-diamino 1 - ([ 3-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1 isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3,4,5-triamino pyrazole, 3, 5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4 - ([3-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts with an acid.

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

  Among the additional couplers that may be used, mention may especially be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers other than the derivatives of formulas (II) and (III) as defined previously and their addition salts.

  By way of examples, mention may be made of 2-methyl-5-aminophenol, 5-N- (Rh-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol and 3-amino phenol. 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (Rhydroxyethyloxy) benzene, 2-amino-4- ( R-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1 R-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3 hydroxy-pyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (Rhydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis (Rhydroxyethylamino) toluene and their addition salts with an acid.

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

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

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

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

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

  The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

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

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

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

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

  Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (IV): ## STR1 ## The dyeing composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any form another form suitable for dyeing keratinous fibers, and in particular human hair.

  The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers, and the color is revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be carried out from an oxidizing composition on containing, applied simultaneously or sequentially to the composition of the invention. Preferably, this coloration is revealed at neutral pH.

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

  The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred. 10 (IV)

  wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, R, and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

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

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

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

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

  The subject of the present invention is also the use for the oxidation dyeing of keratinous fibers, and in particular human keratinous fibers such as the hair, of a composition as defined above.

  The diamino-N, N-dihydropyrazolone derivatives of formula (I) can be obtained from intermediates and synthesis routes described in the literature and in particular in the following references: J. Het. Chem., 2001, 38 (3), 613-616, Helvetica Chimica Acta, 1950, 33, 1183-1194, J. Org. Chem., 23, 2029 (1958), J.Am.Chem.Soc., 73, 3240 (1951), J.Am.Chem.Soc., 84, 590 (1962), Justus Liebig Ann.Chem., 686 , 134 (1965), Tetrahedron. Lett., 31, 2859-2862 (1973), US4128425 and US 2841584 and the cited references.

  According to these references, the compounds of formula (I) having the radicals R3 and R4 equal to hydrogen atoms can be obtained from the synthesis route shown in scheme A below: EtO

Z

COzEt b,.

  The compounds of which the radicals R 1 and R 2 simultaneously represent a methyl group and the radicals R 3 and R 4 of the hydrogen atoms can be obtained in the following manner: ## STR2 ## inspiring of the method described in Justus Lieb.Ann. Chem., 686, 134 (1965) (Scheme B): N H2N-CO-HN) MnH-NHMe + N, HO N OH Me N Me H2N H2N NH2) see scheme A) N., N.

  The compounds of which the radical R 1 represents a methyl group, R 2 a phenyl radical, and the radicals R 3 and R 4 of the hydrogen atoms can be obtained by drawing on the method described in US Pat. described in J.Org.Chem., 23, 2029 (1958), J.Am.Chem.Soc., 73, 3240 (1951) (Scheme C): H2NOC MeNH-NHPh, Me Me Ph Ph N H N 2) see scheme A ## STR2 ## The compounds whose radicals R 1 and R 2 together form a 5-membered ring and whose radicals R 3 and R 4 represent Hydrogen can be obtained by following the method described in J. Het Chem., 2001, 38 (3), 613-616 (Scheme D): 1- BrBr Br NaOH, PTC + 2-H tBuOOC-N N COOtBu> O

H H

  3- HOzCCN, DCC 4-EtOH, HCl, reflux diagram D According to a different process, the compounds of formula (I) can be obtained according to the synthesis illustrated in scheme E: R1HN-NHRz a + NHZ EjCOzEt ji R1 R1 h diagram According to this method, the following steps are carried out: a) step 1: reacting a compound of R1HN-NHR2 to R3R4N N R3R4N) N, R2, N, R2

N N

  see diagram A N-Ar H2N HzN Ar-NH, NaNO2 reduction, N, O R2 2 N -N, ONH + B f

N R1 Ç _3 ..

  EtO NH2CO2Et b with a compound b: R1 to obtain a 5-amino-1,2dihydro-pyrazol-3-one compound: HZN

C

  b) step 2: the derivative ç thus obtained is reacted with an aryldiazonium salt (Ar-NH 2, NaNO 2, H +) to obtain an azo compound f: N, Ar R 1 10 fc) step 3: a step of functionalizing the primary amine group of the resulting azo compound f to obtain a following compound: R1 d) step 4: performing a reduction reaction of the azo compound f or g to obtain, respectively, a compound e or h amine: N-Ar

N e h R1 R1

  The optional step of functionalization of the primary amine group at position 5 to the secondary and tertiary amine NR 3 R 4, to obtain the compounds g, is carried out according to the conventional methods of organic synthesis (alkyl halide, alkyl O-sulphonate, trialkylammonium d alkyl, reductive amination, etc ... see for example Advanced Organic Chemistry, 3rd Edition, 1985, J. March, Willey Interscience).

  The reduction of the azo group leads to compounds e and h according to the invention.

  The reduction step is carried out in a conventional manner, for example by carrying out a hydrogenation reaction by heterogeneous catalysis in the presence of Pd / C, Pd (II) / C, Ni / Ra, etc., or else by carrying out a reduction reaction by a metal, for example by zinc, iron, tin, etc. (See Advanced Organic Chemistry, 3rd Edition, J. March, 1985, Willey Interscience and Reduction in Organic Chemistry, M. Hudlicky, 1983, Ellis Horwood Chemical Science Series).

  According to another method, the 2,3-diamino-6,7-dihydro-1H, 5Hpyrazolo [1,2-a] -pyrazol-1-one and 2,3-diamino-5,6,7,8 derivatives 1-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one are obtained according to the synthesis illustrated in scheme F: R 11

XOH

Rio Rio Rio de Janeiro

HO

  According to this method, the following steps are carried out: a) step 1: a following compound is reacted: ## STR1 ## wherein a compound a2 is used; :

OH a2

to obtain a compound a3:

HO a3

  wherein: the radical R10 represents a hydrogen atom, a carboxy; a carboxamido; a C1-C4 alkyl radical optionally substituted by one or more hydroxyl, amino, (di) -alkylamino, alkoxy, carboxy or sulphonyl radicals; the radicals R and R12 represent, independently of one another, hydrogen and halogen atoms; amino radicals; (Di) alkyl (C1-C4) amino; hydroxy; carboxy; carboxamido; (C1C2) alkoxy; C1-C4 alkyl radical optionally substituted by one or more hydroxyl, amino, (di) alkylamino, alkoxy, carboxy or sulphonyl radicals; X represents a halogen atom or an alkyl sulphonate; r is an integer between 1 and 3.

  b) step 2: the compound a3 is reacted with an amine of formula NHR3R4 to obtain a compound a4:

HO

  c) step 3: the compound a4 is reacted with at least one alkylsulfonyl, arylsulfonyl or perfluoroalkylsulfonyl halide R-O2S-X1 (R represents an alkyl, an aryl or a perfluoroalkyl, X1 represents a halogen), in a solvent with a boiling point of between 60 ° C. and 190 ° C. to obtain a compound a5:

R-SOZ O

  d) step 4: the resulting compound a5 is then heated in a solvent of boiling point between 60 C and 190 C to obtain a compound a6: e) step 5: The compound a6 obtained is reduced to obtain the compound a7 of Formula (V): Formula (V) More particularly, according to this process, 3,5-dibromo-4-nitropyrazole a1, obtained for example according to the method described in DE 4234885, reacts with reagent a2, preferably in a solvent with a boiling point of between 60 ° C. and 190 ° C. By way of example, mention may be made of pentanol, dimethylformamide and N-methylpyrrolidine. More particularly, the reaction is carried out in the presence of an organic or inorganic base, such as, for example, sodium carbonate, sodium hydroxide, sodium acetate or triethylamine. The temperature of the reaction medium is advantageously maintained between 60 ° C. and 160 ° C., preferably between 80 ° C. and 120 ° C.

  The 1-hydroxyalkyl-3,5-dibromo-4-nitropyrazole a3 is preferably isolated by precipitation or crystallization after adding ice to the reaction medium.

  In step 2, the derivative a 3 is reacted with an amine NHR 3 R 4, preferably in a solvent with a boiling point of between 60 ° C. and 190 ° C., such as, for example, butanol, pentanol or dimethylformamide. The temperature is more particularly between 60 ° C. and 160 ° C., preferably between 80 ° C. and 120 ° C. After consumption of the reagents, the compound 5-amino-4-nitro-3-bromo-1-hydroxyalkylpyrazole a4 is isolated by precipitation or crystallization with water.

  According to step 3, the derivative a5 is obtained by reaction of the alcohol a4 and an alkylsulfonyl, arylsulfonyl or perfluoroalkylsulfonyl halide. The reaction is preferably carried out in an aprotic solvent such as, for example, tetrahydrofuran or dioxane. The reaction advantageously takes place at a temperature of between -20 ° C. and 60 ° C., preferably between 0 ° C. and 25 ° C. Furthermore, this step takes place in the presence of an organic or inorganic base such as, for example, potassium carbonate. triethylamine, N-methylmorpholine. After disappearance of the reagents, the compound a5 is isolated by precipitation or crystallization in water.

  The sulphonate a5 obtained at the end of step 3 is put in step 4 in solution or in dispersion in a solvent with a boiling point of between 60 ° C. and 190 ° C., preferably between 90 ° C. and 140 ° C. C. The temperature of the reaction medium is then brought between 90 ° C. and 140 ° C., preferably between 105 ° C. and 125 ° C. until the total consumption of the α5-sulfonate is reached. After returning to ambient temperature, the compound perhydropyrazolo [1,2-a] pyrazol-1-one (r = 1), perhydro-pyridazino [1,2-a] pyrazol-1-one (r = 2) or perhydro-diazepino [1,2-a] pyrazolone (r = 3) a6 crystallizes and is isolated by conventional methods of organic synthesis.

  The final compound a7 according to the invention is obtained, in a step 5 by reduction of the a6 nitro derivative, the reduction methods used being for example a hydrogenation by heterogeneous catalysis in the presence of Pd / C, Pd (II) / C, Ni / Ra, etc ... or else such as a reduction reaction by a metal, for example by zinc, iron, tin, etc., (see Advanced Organic Chemistry, 5th edition, J. March, 1985, Willey Interscience and Reduction in Organic Chemistry, M. Hudlicky, 1983, Ellis Horwood Chemical Science Series).

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

EXAMPLES

  EXAMPLE 1 Synthesis of 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolof-1,2-alpvrazol-1-one dichlorhydrate Br NO2 Br NO2 0 / BnNH2 / + BrOH N Br 'NN O NO2 Br NO2 \ / \ / HZ, Pd-C NNH 0 NNNH / Ph J \ - Ph 2HCI OMs -Step 1: synthesis of 3- (3,5-dibromo-4-nitro-1H-pyrazol) 1-yl) propan-1-ol 1 In a three-necked 500 ml, 0.369 mole of sodium acetate is introduced into a solution of 0.184 mol of dibromonitropyrazole in 250 ml of N-methylpyrrolidone and the reaction medium is brought to 80 ml. C.

  At this temperature, 0.369 moles of 3-bromo-propanol are added dropwise. This temperature is maintained for 5 hours.

  After cooling to room temperature, the medium is poured onto ice with stirring.

  3- (3,5-Dibromo-4-nitro-1H-pyrazol-1-yl) propan-1-ol 1 precipitates. It is drained, dried and obtained with a yield of 75%.

  The mass of the expected compound C6H7Br2N303 is detected by mass spectrometry.

J

NH

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are consistent with the expected structure.

  Step 2: Synthesis of 3- [5- (benzylamino) -3-bromo-4-nitro-1H-pyrazol-1-yl] propan-1-ol In a 500 ml three-necked flask containing 150 ml of ethanol, 0.135 was dispersed. mole of 3- (3,5-dibromo-4-nitro-1H-pyrazol-1-yl) propan-1-ol, heated at 60 ° C, then added 0.825 moles of benzylamine in 30 minutes.

  After 6 hours at 60 ° C., the reaction medium is cooled to room temperature.

  3- [5- (Benzylamino) -3-bromo-4-nitro-1H-pyrazol-1-yl] propan-1-ol 2 is precipitated by pouring the reaction medium into 1 liter of ice with stirring. After drying and drying under vacuum in the presence of P 2 O 5, the compound 2 is isolated in a yield of 90%.

  Theoretical: C43.96 H4.26 N15.77 013.51 Br22.50 measured: C44.09 H4, 22 N15, 44.014.37 Br21.50 -Step 3: synthesis of 3- [5- (benzylamino) -3 In a 500 ml three-necked flask containing 200 ml of THF, 0.126 mol of 3- [5 (benzylamino) -3-bromo-4-nitro are introduced with stirring in a 500 ml three-neck flask containing 200 ml of THF. -1H-pyrazol-1-yl] propan-1-ol 2 and 15.82 ml of triethylamine. The resulting mixture is then cooled to 5 ° C. and 0, 126 moles of mesyl chloride are cast in 45 minutes.

  The reaction medium is maintained at this temperature for 2 hours, then the 3- [5- (benzylamino) -3-bromo-4-nitro-1H-pyrazol-1-yl] propylmethanesulfonate 3 is precipitated by pouring the reaction medium on 800 ml of the ice cream.

  After filtration, the solid is washed extensively with water and with diisopropyl ether. The drying is carried out under vacuum in the presence of P2O5. The yield of this step is 94%.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  Elemental analysis: to the expected structure.

  Elemental analysis: Theory: C38.81 H3.96 N12.93 018.46 S7.40 Br18.44 Measured: C39.03 H3.91 N12.83 018.52 S7.29 Br18.26 -Step4: synthesis of the 3 - (benzylamino) -2-nitro-6,7-dihydro-1H, 5H-pyrazolo [1,2-alpyrazol-1-one 4 In a 500 ml three-necked flask containing 300 ml of pentanol, the mixture is dispersed with stirring 0.1 mole of 3- [5- (benzylamino) -3-bromo-4-nitro-1H-pyrazol-1-yl] propyl methanesulfonate 3 and the reaction medium at 130 ° C. for 2 hours.

  After cooling to room temperature, the solid formed is filtered off with suction, washed with diisopropyl ether and dried under vacuum in the presence of P2O5. 3- (Benzylamino) -2-nitro-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 4 is obtained in a yield of 86%.

  NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C6H11N40 is detected by mass spectrometry.

  Elemental analysis: Theory: C56.72 H5.49 N20.36 017.44 Measured: C56.68 H5.13 N20.38 017.69 -Step 5: synthesis of 2,3-diamino-6,7-dihydro dihydrochloride 1H, 5H-pyrazolo [1,2-alpyrazol-1-one In a 1-liter autoclave containing 800 ml of ethanol, 20 g of 3- (benzylamino) -2-nitro-6,7-dihydro-1H are introduced. , 5H-pyrazolo [1,2-a] pyrazol-1-one 4 and 4 g of 5% palladium on carbon. The reduction is then carried out under a hydrogen pressure of 8 bar and at a temperature of between 50 ° C. and 100 ° C. (stirring of between 1000 and 2500 rpm).

  The mass of the expected compound C14H17BrN405S is detected by mass spectrometry.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are compliant After 4 hours of reaction, it no longer consumes hydrogen and the medium is cooled to 20 C.

  The catalyst is removed under nitrogen by filtration, and then hydrochloric ethanol is added to the filtrate. The crystallized product is drained, washed with diisopropyl ether and then dried under vacuum in the presence of P2O5. 2,3-Diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one dihydrochloride is obtained in a yield of 89%.

  The mass of the expected compound is detected by mass spectrometry.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  Elemental analysis: Theoretical: C31.73 H5.33 N24.67 07.07 C131.22 Measured: C31.45 H5.20 N24.62 07.24 C130.86 Example 2: Synthesis of 2-amino-3- dichlorhydrate (Ethylamino) -6,7-dihydro-1H, 5H-pvrazolof 1,2-alpvrazol-1one 9 + Br 6 OH-MsO -Step 2: Synthesis of 3- [3-bromo-5- (ethylamino) 4-nitro-1H-pyrazol-1-ylpropan-1-ol In a tricolor, with stirring, 15 mmol of 3- (3,5-dibromo-4-nitro-1H-pyrazol-1-yl) propanin are introduced. 1-ol in 30 ml of ethanol. The homogeneous medium is heated to 75 ° C., then 93 mmol of ethylamine are poured dropwise and stirring is continued for four hours.

  After cooling to room temperature, the medium is poured onto ice and the 3- [3-bromo-5- (ethylamino) -4-nitro-1H-pyrazol-1-yl] propan-6-ol precipitates.

  The yellow solid is drained and then washed extensively with water and diisopropyl ether. The drying is carried out under vacuum in the presence of P2O5. The recovered mass is 3.6 g.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C $ H13BrN403 is detected by mass spectrometry.

  Step 3: Synthesis of 3- [5- (ethylamino) -3-bromo-4-nitro-1H-pyrazol-1-ylpropyl methanesulphonate 7 Into a 100 ml tricol, containing 30 ml of THF, with stirring, 11.2 g of mmol of 3- [3-bromo-5- (ethylamino) -4-nitro-1H-pyrazol-1-yl] propan-1-ol 6 and 1.6 ml of triethylamine. The orange homogeneous mixture obtained is cooled to 0 ° C. and 1.44 ml of mesyl chloride are cast in 20 minutes.

  The reaction medium is maintained at this temperature for 2 hours and then the 3- [5- (ethylamino) -3-bromo-4-nitro-1H-pyrazol-1-yl] propylmethanesulfonate 7 is precipitated by pouring the reaction medium over 500 ml of ice.

  The yellow solid is drained and then washed extensively with water and diisopropyl ether; the drying is carried out under vacuum in the presence of P2O5. The recovered mass is 3.1 g.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C9H15BrN4O5S is detected by mass spectrometry.

  Step 4: Synthesis of 3- (ethylamino) -2-nitro-6,7-dihydro-1H, 5Hpyrazolo [1,2-alpyrazol-1-one 8 In a 50 ml three-necked flask containing 20 ml of pentanol, the mixture is dispersed with stirring 8 mmol of 3- [5- (ethylamino) -3-bromo-4-nitro-1H-pyrazol-1-yl] propyl methanesulfonate 7, and the reaction medium at 130 C for 2 hours.

  After cooling to room temperature, the solid formed is filtered off and then washed with diisopropyl ether.

  After drying under vacuum in the presence of P 2 O 5, 1.46 g of 3 (ethylamino) -2-nitro-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 8 are obtained.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound is detected by mass spectrometry.

  Step 5: Synthesis of 2-amino-3- (ethylamino) -6,7dihydro-1H, 5H-pyrazolo [1,2-alpyrazol-1-one dihydrochloride 9 In a 300 ml autoclave containing 200 ml of ethanol, 1.45 g of 3- (ethylamino) -2-nitro-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 8 and 300 mg of palladium-on-carbon were introduced. 5%. The reduction is carried out under a hydrogen pressure of 8 bars at a temperature of 60 ° C. (stirring of 1700 rpm).

  After 2 hours of reaction, there is no more consumption of hydrogen and the medium is cooled to 20 C.

  The catalyst is removed by filtration under nitrogen and the filtrate is diluted with 100 ml of hydrochloric isopropyl ether.

  The pale yellow solution is evaporated to dryness and the solid is taken up with an ethanol / isopropyl ether mixture. 2-Amino-3 (ethylamino) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one dihydrochloride precipitates; it is drained and after drying under vacuum in the presence of P 2 O 5, 1.18 g of 2-amino-3- (ethylamino) -6,7-dihydro-1H, 5Hpyrazolo [1,2-a] pyrazol dihydrochloride are recovered. 1-one 9.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C $ H14N40 is detected by mass spectrometry.

  Example 3: 2-Amino-3- (isopropylamino) -6,7-dihydro-1H, 5H-pyrazololl, 2-alpyrazol-1-one dihydrochloride Step 2: 3- [3-bromo-5- (isopropylamino) -4-nitro-1H-pyrazol-1-yllpropan-1ol In a tricolor, with stirring, 15 mmol of 3- (3,5dibromo) are added. 4-nitro-1H-pyrazol-1-yl) propan-1-ol in 30 ml of ethanol. The homogeneous medium is heated to 75 ° C., then 93 mmol of isopropylamine are poured dropwise while maintaining the stirring for four hours.

  After cooling to room temperature, the medium is poured onto ice and neutralized with hydrochloric acid. 3- [3bromo-5- (isopropylamino) -4-nitro-1H-pyrazol-1-yl] propan-1-ol is extracted with dichloromethane.

  After drying the organic phase over sodium sulphate and removing the solvent by evaporation under vacuum, 4.37 g of 3- [3-bromo-5 (isopropylamino) -4-nitro-1H-pyrazol-1-yl are obtained. ] propan-1-ol 10.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C9H15BrN4O3 is detected by mass spectrometry.

  Step 3: Synthesis of 3- [5- (isopropylamino) -3-bromo-4-nitro-1H-pyrazol-lyllpropyl methanesulfonate 11 Into a 50 ml three-necked flask containing 20 ml of THF, 13 g of stirring are introduced. 7 mmol of 3- [3-bromo-5 (isopropylamino) -4-nitro-1H-pyrazol-1-yl] propan-1-ol and 1.94 ml of triethylamine. The orange homogeneous mixture thus obtained is cooled to 0 ° C. and 1.76 ml of mesyl chloride are cast in 20 minutes.

  The reaction medium is maintained at this temperature for 2 hours, then the 3- [5- (ethylamino) -3-bromo-4-nitro-1H-pyrazol-1-yl] propylmethanesulphonate 11 is precipitated by pouring the reaction medium on 500 ml of ice cream

  The yellow solid is drained, then washed extensively with water and with petroleum ether, the drying is carried out under vacuum in the presence of P2O5. The recovered mass is 4.2 g.

  NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are consistent with the expected structure.

  The mass of the expected compound is detected by mass spectrometry.

  Step 4: Synthesis of 3- (Isopropylamino) -2-nitro-6,7-dihydro-1H, 5Hpyrazolo [1,2-alpyrazol-1-one 12 In a 50 ml tricol, the mixture is dispersed, with stirring 10 mmol of 3- [5- (isopropylamino) -3-bromo-4-nitro-1Hpyrazol-1-yl] propylmethanesulfonate 11 in 20 ml of pentanol and heated at 130 ° C. for 2 hours.

  After cooling to room temperature, the resulting solid is sintered and washed with diisopropyl ether.

  After drying under vacuum in the presence of P 2 O 5, 1.71 g of 3- (isopropylamino) -2-nitro-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 12 are obtained.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C9H14N403 is detected by mass spectrometry.

  Step 5: Synthesis of 2-amino-3- (isopropylamino) -6,7dihydro-1H, 5H-pyrazolo [1,2-alpyrazol-1-one dihydrochloride 13 In a 300 ml autoclave containing 200 ml of ethanol 1.70 g of 3 (isopropylaminoamino) -2-nitro-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 12 and 300 mg of 5% palladium-on-charcoal are introduced. . The reduction is carried out at a temperature of 60 ° C. and at a hydrogen pressure of 6 bars (stirring at 2000 rpm).

  After 2 hours of reaction, it no longer consumes hydrogen and the medium is cooled to 20 C.

  The catalyst is removed by filtration under nitrogen after cooling to room temperature and hydrochloric isopropyl ether is added.

  The pale yellow solution is evaporated to dryness, then the solid is taken up in 50 ml of diisopropyl ether saturated with hydrochloric acid, the precipitate is recovered by spinning. After drying under vacuum in the presence of P 2 O 5, 1.5 g of 2-amino-3- (isopropylamino) -6,7-dihydro-1H, 5Hpyrazolo [1,2-a] pyrazol-1-one dihydrochloride are added. isolated.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C9H16N40 is detected by mass spectrometry.

  Example 4: 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolof1,2-alpvrazol-1-one 17 + BrOH dichlorhydrate

HO OH 14

  Step 2: 3- (3-Bromo-4-nitro-5- (pyrrolidin-1-yl) -1H-pyrazol-1-yl) propan-1-ol 14 In a tricol, under After stirring, 15 mmol of 3- (3,5-dibromo-4-nitro-10H-pyrazol-1-yl) propan-1-ol are introduced into 20 ml of isopropanol. The homogeneous medium is heated to 75 ° C., then 90 mmol of pyrrolidine are poured dropwise and stirring is maintained for two hours.

  After cooling to room temperature, the mixture is poured onto ice and neutralized with hydrochloric acid. 3- (3bromo-4-nitro-5- (pyrrolidin-1-yl) -1H-pyrazol-1-yl) propan-1-ol 14 is extracted with dichloromethane.

  After drying the organic phase over sodium sulphate and distilling off the solvent by evaporation under vacuum, 4.8 g of 3- (3-bromo-4-nitro-5- (pyrrolidin-1-yl) -1 H-pyrazol are obtained. 1-yl) propan-1-ol 14.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C1oH17BrN40 is detected by mass spectrometry.

  Step 3: Synthesis of 3- (3-bromo-4-nitro-5- (pyrrolidin-1-yl) -1H-pyrazolyl) propylmethanesulfonate In a 100 ml three-necked flask containing 50 ml of THF, with stirring, 30 mmol 3- (3-bromo-4-nitro-5 (pyrrolidin-1-yl) -1H-pyrazol-1-yl) propan-1-ol and 4.25 ml of triethylamine. The orange homogeneous mixture obtained is cooled to 0 ° C. and 2.32 ml of mesyl chloride are cast in 20 minutes.

  The reaction medium is maintained at this temperature for 2 hours and then the 3- (3-bromo-4-nitro-5- (pyrrolidin-1-yl) -1H-pyrazol-1-yl) propylmethanesulfonate is precipitated by pouring the medium reaction on ice.

  The solid is drained and then dried under vacuum in the presence of P2O5. The recovered mass is 9.3 g.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The expected compound C11H19BrN4O3S mass is detected by mass spectrometry.

  Step 4: Synthesis 2-nitro-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5Hpyrazolo [1,2-alpyrazol-1-one 16 In a 250 ml tricol, the following are introduced: with stirring, 22.5 mmol of 3- (3-bromo-4-nitro-5- (pyrrolidin-1-yl) -1 Hpyrazol-1-yl) propylmethanesulfonate in 100 ml of pentanol. The medium thus obtained is brought to 130 ° C. for 2 hours.

  After cooling to room temperature, 2-nitro-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 16 is extracted with dichloromethane.

  After drying the organic phase over sodium sulphate and distilling off the solvent in vacuo, 1.2 g of 2-nitro-3-pyrrolidin-1-yl-6,7-dihydro-1H, 5H-pyrazolo [1,2- a] pyrazol-1-one 16.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C10H14N403 is detected by mass spectrometry.

  Step 5: Synthesis of 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pvrazolo [1,2-alpvrazol-1-one dichlorhydrate 17 In a 300 ml autoclave containing 200 ml of ethanol are charged with 1.1 g of 2-nitro-3 (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one 16 and 300 mg of 5% palladium on carbon. The reduction is carried out under agitation of 2000 rpm, under a temperature of 60 C and under a hydrogen pressure of 6 bar.

  After 2 hours of reaction, it no longer consumes hydrogen and the medium is cooled to 20 C.

  The catalyst is removed by filtration under nitrogen after cooling to room temperature and hydrochloric isopropyl ether is added.

  The pale yellow solution is evaporated to dryness, then the solid is taken up in 50 ml of diisopropyl ether saturated with hydrochloric acid, the precipitate is recovered by spinning. After drying under vacuum in the presence of P 2 O 5, 1.5 g of 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol dihydrochloride are obtained. 1-one 5 17.

  The NMR analyzes (1H 400 MHz and 13C 100.61 MHz DMSO d6) are in accordance with the expected structure.

  The mass of the expected compound C1oH16N40 is detected by mass spectrometry.

  Example 5 Synthesis of 2,3-diamino-6,7-dihydro-1H, 5H-pvrazolof 1,2-alpvrazol-1-one dimethanesulphonate

O NHZ

O

  N 2 O = S OH NH CH 2 Synthesis of 3-amino-2-nitroso-6,7-dihydro-1H, 5Hpyrazolo [1,2-alpvrazol-1-one: 2 In a 500 ml tricol, one dissolved, with stirring, at room temperature, 43 g (0.245 mol) of 3-amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one hydrochloride in a mixture of 180 ml of water and 35 ml of 35% hydrochloric acid.

  It is cooled to 0 ° C. and a solution of 17.3 g of sodium nitrite (0.25 mol) in 20 ml of water is added dropwise in 30 minutes. The temperature of the reaction medium is maintained between 0 and +5 C throughout the duration of the addition and for one hour after the end of the addition.

  The reaction medium is brought to pH 8 by addition of sodium hydroxide, with stirring, while maintaining the temperature between 0 and 5 ° C. 3-amino-2-nitroso-6,7-dihydro-1H, 5H-pyrazolo [1,2 a] pyrazol-1-one 2 precipitates in the form of a red orange solid which is filtered on n-4 sintered glass, impasted in the minimum of 2-propanol, washed with diisopropyl ether and dried under vacuum in the presence of phosphorus pentaoxide. 35 g of orange-red product are thus obtained (yield: 85%).

  The NMR (1H 400 MHz and 13C 100.61 MHz DMSO d6) and mass spectra are consistent with the expected structure 2.

  Reduction O O NaNO2 HCI-H2O <N, NNH2, HCI Base <NN

NO

  Synthesis of 2,3-diamino-6,7-dihydro-1H, 5Hpyrazolo [1,2-alpyrazol-1-one: 3-dimethyesulfonate In a 1-liter autoclave, 33.6 g (0.2 mol ) of 3-amino-2-nitroso-6,7-dihydro-1H, 5Hpyrazolo [1,2-a] pyrazol-1-one 2, 500 ml of ethanol and 6 g of 5% palladium on carbon containing 50 % of water.

  The medium is purged 3 times with nitrogen and then 3 times with hydrogen and the temperature of the mixture is brought to 40 C.

  The reduction is carried out in two hours under a pressure of 8 bar. This reduction is exothermic and the temperature itself reaches 70 C.

  The temperature is allowed to drop to 50 ° C. and the catalyst is then filtered on a press filter under a stream of nitrogen.

  The filtrate is poured into a mixture of 50 ml of ethanol and 40 ml of methanesulfonic acid, while cooling to 0 ° C. 2,3-Diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-dimethyesulphonate] a] pyrazol-1-one 3 crystallizes in the form of a pale yellow solid which is drained on sintered glass n 4, washed with diisopropyl ether and then with petroleum ether and finally dried under vacuum in the presence of pentaoxide of phosphorus. 43 g of pale yellow solid are thus obtained (yield: 65%).

  The NMR (1H 400 MHz and 13C 100.61 MHz DMSO d6) and mass spectra are consistent with the expected structure 3.

  Elemental analysis: Theory: C27.74 H5.23 N16, 17 032.33 S18.51 Measured: C27.16 H5.22 N15.63 032.81 S18.64 Example 6: Synthesis of 2,3-diaminohydrochloride 5,6,7,8-tetrahydro-1H-pyrazolof1,2-alpvridazin-1-one. HCI o

  O H Z) \ \ OBr (CH) Br CIHNHN HZq /, N,

H

  a /, NNHZ N'NToluene IV_E_ I 1 H NaOH

A B

  Synthesis of di-tert-butyl tetrahydropyridazine-1,2-dicarboxylate: In a 250 ml three-necked flask equipped with a condenser, a thermometer and a dropping funnel, 50 ml of toluene are introduced with mechanical stirring. 5 g (21.5 mmol) of N, N'-di-tert-butoxycarbonylhydrazide, 680 mg of tetraethylammonium bromide and 25 mol% or 50%.

  The heterogeneous medium is heated to 100 ° C. and 1.4-dibromobutane is then added dropwise over 15 minutes.

  The reaction medium is heated at 100 ° C. for 3 days. After cooling, 100 ml of ethyl acetate are added and transferred to a separatory funnel. The organic phase is washed with 4 times 70 ml of saturated aqueous sodium carbonate solution, then with 4 × 70 ml of water and finally with 4 × 70 ml of saline water. The organic phase is dried over sodium sulfate and the solvent is evaporated under vacuum. A colorless oil is thus obtained which crystallizes in a white solid.

  A mass of 6.1 g is recovered (yield: 99%).

  The NMR (1H 400 MHz and 13C 100.61 MHz DMSO d6) and mass spectra are in accordance with the expected structure A. Synthesis of hexahydropyridazine dihydrochloride: B In a 100 ml three-necked flask equipped with a refrigerant and a thermometer, is introduced with mechanical stirring 5.9 g of compound A in 50 ml of 3/1 mixture of dioxane and 35% hydrochloric acid.

  The colorless solution obtained is stirred at ambient temperature for 3 hours and then the reaction medium is diluted with diisopropyl ether. The solvents are evaporated under vacuum. The pasty residue obtained is taken up in an ether / ethanol mixture. After filtration of the solid and drying under vacuum, 1.39 g of white solid are obtained.

  The NMR (1H 400 MHz and 13C 100.61 MHz DMSO d6) and mass spectra are consistent with the expected structure B. Synthesis of 3-amino-5,6,7,8-tetrahydro-1H-pyrazolofl, 2-alpyridazin 1-one: C In a 25 ml three-necked flask equipped with a condenser and a thermometer, 7.5 ml of ethanol, 1.5 ml of triethylamine and 0.73 ml of 3-amino acid are introduced with mechanical stirring. -3-ethoxyacrylique. 500 mg of hexahydropyridazine dihydrochloride (compound B) are then added and the mixture is stirred for 3 hours at room temperature.

  The insoluble material is filtered off and the solvent is distilled under vacuum. The solid is taken up by the minimum of water, filtered and dried under vacuum. 0.9 g of slightly yellow powder are thus obtained.

  The NMR (1H 400 MHz and 13C 100.61 MHz DMSO d6) and mass spectra are consistent with the expected structure C. Synthesis of 3-amino-2-nitroso-5,7,7,8-tetrahydro-1H- In a 50 ml three-necked flask equipped with a condenser and a thermometer, 20 ml of 35% hydrochloric acid and 1 g of 3-pyridinyl are introduced under mechanical stirring. amino5,6,7,8-tetrahydro-1H-pyrazolo [1,2-a] pyridazin-1-one (compound C).

  It is cooled to 0.degree. C. and a solution of 675 mg sodium nitrite in 5 ml of water is poured while maintaining this temperature. The color of the reaction mixture changes from yellow to orange and a precipitate begins to form.

  In 30 minutes, the reaction is complete and the orange solid is filtered on n-4 sintered glass, washed with water and then dried under vacuum. The yield is 78.3%.

  The NMR (1H 400 MHz and 13C 100.61 MHz DMSO d6) and mass spectra are consistent with the expected structure D. Synthesis of 2,3-diamino-5,6,7,8-tetrahydro-1H hydrochloride In a 300 ml autoclave containing 250 ml of ethanol, 1.3 g of 3-amino-2-nitroso-5,6,7,8-tetrahydro are introduced into the 300 ml autoclave containing 250 ml of ethanol. -1H-pyrazolo [1,2-a] pyridazin-1-one (compound D) and 250 mg of 5% palladium on charcoal. The reduction is carried out with stirring at 2000 rpm, at a temperature of 60 ° C. and under a hydrogen pressure of 6 bar.

  After 2 hours of reaction, there is no more consumption of hydrogen and the medium is cooled to 20 C.

  The catalyst is removed by filtration under nitrogen after cooling to room temperature and the solution is poured over 75 ml of hydrochloric dioxane.

  The solution thus obtained is evaporated to a slightly yellow powder which is taken up in diisopropyl ether.

  The solid is recovered by filtration. After drying under vacuum in the presence of phosphorus pentoxide, 1.1 g of 2,3-diamino-5,6,7,8,5-tetrahydro-1H-pyrazolo [1,2-a] pyridazinedihydrochloride are obtained. 1-one.

  The NMR (1H 400 MHz and 13C 100.61 MHz DMSO d6) and mass spectra are in accordance with the expected structure E. EXAMPLE 7 Synthesis of 4-Amino-1,2-diethyl-5-pyrrolidin-1 hydrochloride Step 1: Synthesis of 1, 2-diethylpyrrolidine-3,5-dione In a 3,000 ml tricol with a thermometer and with magnetic stirring, are introduced successively under a temperature gradient of 200.degree. 100 g of diethylhydrazine dihydrochloride (0.63 mol) in 1000 ml of dichloromethane, 85.3 g of malonic acid (0.82 mol, 1.3 eq), 196 g of hydroxybenzotriazole (1.45 mol 2.3 eq), 278 g of 1- (3-dimethylaminopropyl) -3-ethyl-carbodiimide, hydrochloride (EDCI, 1.45 moles, 2.3 eq.).

  The reaction medium is then cooled between 0 ° C. and 5 ° C. 407 g of N, N-diisopropylethylamine (3.14 mol, 520 ml: 5 eq) are then slowly added thereto. At the end of the addition, the reaction medium, which has become homogeneous, is left stirring at room temperature. After one night at room temperature, the reaction is complete.

  The reaction medium is washed with three times 600 ml of deionized water. The organic phase is dried over sodium sulfate, filtered and concentrated under vacuum to give 46 g of crude product. The pyrazolidine-dione being soluble in an aqueous medium, the aqueous phase is thus concentrated to dryness and then taken up in 800 ml of a 1N hydrochloric acid solution. The precipitate formed is filtered and the aqueous phase is extracted three times with 1300 ml. dichloromethane. The combined organic phases are dried over sodium sulfate, filtered and concentrated in vacuo to afford 67.5 g of crude product.

  1,2-diethylpyrazolidine-3,5-dione is thus obtained in the form of a yellow solid with a yield of 40% (39.5 g).

  Step 2: Synthesis of 1,2-diethyl-3-chloro-5-pvrazolone In a three-necked 500 ml equipped with a condenser and a magnetic stirrer, 30 g of 1 g are introduced under a nitrogen atmosphere. 2 g of 1,2-diethylpyrazolidine-3,5-dione (0.19 mol) dissolved in 200 ml of toluene and 35.8 ml of trichlorophosphine oxide (258.9 g, 0.38 mol, 2 eq. ).

  The reaction medium is refluxed with toluene and the reaction is monitored by TLC (dichloromethane / methanol 95/5). The reaction medium, initially in the form of a paste, is homogenized at reflux and then becomes biphasic.

  After one hour of reflux, the reaction is hydrolysed at 0 C by very slow addition of 100 ml of deionized water. After decantation, the toluene phase is separated from the aqueous phase. The aqueous phase is washed with 50 ml of toluene and then brought to pH 12 with 184 ml of a 35% sodium hydroxide solution. The formation of a precipitate is observed. The aqueous phase is brought to 100 ° C. for 10 minutes and the precipitate is solubilized. The reaction medium then has two phases. The upper phase of brown coloration is separated after hot settling. This upper phase is solubilized with 200 ml of dichloromethane, washed with once 50 ml of deionized water, dried over sodium sulfate and concentrated in vacuo to give 20.5 g of a brown oil.

  A precipitate is formed in the lower aqueous phase upon return to ambient temperature. After filtration on sintered, the precipitate is rinsed with water and the filtrate is extracted three times with 300 ml of dichloromethane. The dichloromethane phase is dried over sodium sulphate and concentrated in vacuo to give 5.5 g of brown crystals.

  The oil and the brown crystals are combined, grafted onto silica and chromatographed on silica gel (40-60 μm, 2000 g) by an elution gradient 1) Dichloromethane 100 (13 liters) 2) Dichloromethane / MeOH 99.5 / 0.5 (0.8 liters) 3) Dichloromethane / MeOH 99/1 (8 liters) expected product + 15% impurity m = 6.6 g 4) Dichloromethane / MeOH 98.5 / 1.5 (35 liters) expected product (14.7 g) 1,2-diethyl-3-chloro-5-pyrazolone is thus obtained in the form of yellow crystals with a yield of 44%.

  Step 3: Synthesis of 1,2-Diethyl-5-pyrrolidin-1-yl-1,2-dihydro-pvrazol-3one In a reactor, 2.5 ml of the Biotage initiator microwaves are charged with 1 g of 5-chloro 1,2-diethyl-1,2-dihydro-pyrazol-3-one (5.7.10-4 mol), to which 2 ml of pyrrolidine (4.2 eq) are added.

  Operating conditions: microwave at maximum power e = 120 C for 17 min. After 17 minutes, the reaction is complete (TLC monitoring eluent: 90/10 CH 2 Cl 2 / MeOH).

  1 ml of demineralized water are then added to the reaction medium, and the whole is then transferred to a separating funnel. The aqueous phase is extracted with four times 10 ml of dichloromethane. The organic phases are then combined and dried over anhydrous sodium sulfate, then filtered and evaporated to dryness. 1.2 grams of a brown orange oil are obtained with a yield of 100%.

  NMR (1H 400 MHz DMSO d6) 0.81 (1H, 3H), 0.89 (1H, 3H), 1.88 (1m, 1H), 3.2 (1m, 4H), 3.4 (1m, 4H), 4.4 (1s, 1H) Mass: Analysis made in OpenLynx (FIA / MS).

  The mass mainly detected is in agreement with the expected structure: M = 20 Step 4: Synthesis of 1,2-diethyl-4-nitroso-5-pyrrolidin-1-yl-1,2-dihydro-3H-pyrazol-3-one

NO

J

  1.2 g of 1,2-diethyl-5-pyrrolidin-1-yl-1,2-dihydro-pyrazol-3-one, which has been solubilized in a mixture of 0 g, are introduced into a fully equipped 25 ml three-necked flask. 84 ml of 37% hydrochloric acid and 4 ml of demineralized water.

  The reaction medium is cooled between 0 ° C. and 5 ° C., using an ice-water bath.

  A solution composed of 400 mg of sodium nitrite (5.7 × 10 4 mol) solubilized in 0.6 ml of demineralised water is then added dropwise.

  The reaction medium turns instantly bright red when adding the first drop of the previous mixture.

  After one hour, the reaction is complete.

  The pH is adjusted to about 7-8 with a 30% sodium hydroxide solution and the reaction medium is transferred to a separating funnel. The aqueous phase is extracted with 4 times 10 ml of dichloromethane. The organic phases are combined and dried over anhydrous sodium sulphate and then evaporated to dryness. 1.2 grams of a turquoise powder are obtained with a yield of 89.6%.

  The NMR (400 MHz DMSO d6) and mass spectra are consistent with the expected structure.

  NMR (1H 400 MHz DMSO d6) 0.94 (1H, 3H), 1 (1H, 3H), 2.05 (1m, 4H), 3.51 (1q, 4H), 3.76 (1q, 4H) , 3.94 (1m, 4H) Analysis made in OpenLynx (FIAIMS).

  The mass mainly detected is in agreement with the expected structure. M = 238.

  Step 5: Synthesis of 4-Amino-1,2-diethyl-5-pyrrolidin-1H-1,2-dihydro-pvrazol-3-one hydrochloride: In a three-necked 500 ml fully equipped, 4 grams of zinc are introduced powder (0.06 moles) in 300 ml of absolute ethanol to which 1 ml of acetic acid is added.

  The reaction medium is heated to 40 ° C. and then 1.15 g (4.8 × 10 -3 moles) of 1,2-diethyl-4-nitroso-5-pyrrolidin-1-yl-1,2-dihydro-3H-. pyrazol-3-one are introduced by small spatulas. 4 ml of acetic acid are finally introduced ml per ml and the medium is brought to reflux. The medium is completely soluble and colorless. After 30 minutes, the reaction is complete on TLC according to the eluent ethyl acetate / MeOH 90/10.

  The reaction medium is cooled and then filtered on sinter containing a bed of 545 cellite. The mother liquors are filtered in a flask containing 2.5 ml of cooled 5 N hydrochloric isopropanol. Everything is then evaporated to dryness. The product obtained is a pink powder conforming to NMR and Mass.

  NMR (1H 400 MHz DMSO d6) 0.79 (1H, 3H), 0.96 (1H, 3H), 1.87 (1m, 4H), 3.49 (1q, 2H), 3.59 (1m, 6H) FIA / MS analysis performed via OpenLynx.

  The quasi-molecular ions [M + H] +, [M + Na] +, [2M + H] +, [2M + Na] + of the expected base C H20N40 are mainly detected.

  By reproducing the above steps with the appropriate reagents, 4-amino-5- [3- (dimethylamino) pyrrolidin-1-yl] -1,2-diethyl1,2-dihydro-3H-pyrazol-3-one hydrochloride can be obtained. . 2 HCI

J

EXAMPLES OF STAIN

Example 1

  The following composition 1 was carried out: Oleyl alcohol polyglycerolated with 2 moles of glycerol 4 g Oleyl alcohol polyglycerolated with 4 moles of glycerol (78% M.A.) 5.69 g M.A.

  Oleic acid 3 g Oleic amine 2 EO sold under the name Ethomeen 012 by the company Akzo 7 g Diethylaminopropyl Laurylamino succinamate, 55% sodium salt M.A. 3 g M.A.

  Oleyl alcohol 5 g Oleic acid diethanolamide 12 g Propylene glycol 3.5 g Ethyl alcohol 7 g Dipropylene glycol 0.5 g Propylene glycol monomethyl ether 9 g Sodium metabisulphite in aqueous solution at 35% M A. 0.455 g M.A.

  Ammonium acetate 0.8 g 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, HCl 2.27 g 5,6-dihydroxyindole 1 , 49 g Antioxidant, sequestering qs

Perfume, preservative q.s.

  Ammonia at 20% NH3 10 g Demineralized water qs 100 g Method of application At the time of use, the composition 1 is mixed with 1 part of its volume of 20 volume hydrogen peroxide solution whose pH is equal to 3. A final pH of 9.8 is obtained.

  The mixture obtained is applied to strands of gray hair with 90% natural whites at the rate of 30 g of mixture per 3 g of hair. After 30 minutes of exposure to room temperature, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. Capillary staining is evaluated visually.

  Height of tone Reflection Composition 1 Dark brown Deep iridescent iridescent

Example 2

  The following composition 2 was carried out: Oleyl alcohol polyglycerolated with 2 moles of glycerol 4 g Oleic alcohol polyglycerolated with 4 moles of glycerol (78% M.A.) 5.69 g M.A.

  Oleic acid 3 g Oleic amine 2 EO marketed under the name ETHOMEEN company AKZO 7 g Laurylamino diethylaminopropyl succinamate, 55% sodium salt M.A.

  Oleyl alcohol oleic acid diethanolamide Propylene glycol Ethyl alcohol Dipropylene glycol Propylene glycol monomethyl ether Sodium metabisulphite 35% aqueous solution MA Ammonium acetate 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1 , 2-a] pyrazol-1-one, HCl 5,6-dihydroxyindoline, HBr Antioxidant, sequestering perfume, preservative Ammonia at 20% NH3 Demineralized water 012 by 3gM.A. 5g

  12 g 3.5 g 7 g 0.5 g 9 g 0.455 g MA 0.8 g 2.27 g 2.32 g q.s. qs g

  qsp 100 g Application method At the time of use, the composition 2 is mixed with 1 times its volume of 20 volumes of hydrogen peroxide solution whose pH is equal to 3. A final pH of 9 is obtained, 8.

  The mixture obtained is applied to strands of gray hair with 90% natural whites at the rate of 30 g of mixture per 3 g of hair. After 30 minutes of exposure to room temperature, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

  Capillary staining is evaluated visually.

  Height of tone Reflection Composition 2 Light brown iridescent Violine

Claims (31)

  1. A dyeing composition of keratinous fibers comprising, in a suitable medium: E at least one oxidation base chosen from a diamino-N, N-dihydropyrazolone derivative of formula (I) or one of its salts; 'addition: O NH / 2   Wherein R 1, R 2, R 3 and R 4, which may be identical or different, represent: a linear or branched C 1 -C 10 alkyl radical optionally substituted by one or more radicals chosen from the group consisting of ORS radical, a NR6R7 radical, a carboxy radical, a sulphonic radical, a carboxamido radical CONR6R7, a sulphonamido radical SO2NR6R7, a heteroaryl, an aryl optionally substituted by one or more (C1-C4) alkyl, hydroxy or C1-alkoxy groups. -C 2, amino, (di) (C 1 -C 2) alkylamino; -an aryl radical optionally substituted with one or more (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) alkyl radicals; (C 1 -C 2) amino - a 5- or 6-membered heteroaryl radical, optionally substituted by one or more radicals selected from a (C 1 -C 4) alkyl, (C 1 -C 2) alkoxy radical, R 3 and R 4 may represent also a hydrogen atom, R6, R6 and R7, which may be identical or different, represent: a hydrogen atom; linear or branched C 1 -C 4 alkyl optionally substituted with one or more radicals chosen from a hydroxyl radical, C 1 -C 2 alkoxy radical, carboxamido radical CONR 8 R 9, sulphonyl SO 2 R 8, aryl optionally substituted with a (C 1 -C 4) alkyl, hydroxy or alkoxy radical; C1-C2, amino, (di) (C1-C2) alkylamino; aryl optionally substituted with a (C 1 -C 4) alkyl, hydroxy, C 1 -C 2 alkoxy, amino, (di) (C 1 -C 2) alkylamino; R6 and R7, which may be identical or different, may also represent a carboxamido radical CONR8R9; a sulphonyl radical SO2R8; R8 and R9, identical or different, represent a hydrogen atom; a linear or branched C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C2 alkoxy radicals; R 1 and R 2, on the one hand, and R 3 and R 4, on the other hand, can form, with the nitrogen atom or atoms to which they are attached, a saturated or unsaturated 5- to 7-membered heterocycle, optionally substituted by one or more radicals selected from the group consisting of halogen atoms, amino, (di) (C 1 -C 4) alkylamino, hydroxy, carboxy, carboxamido, (C 1 -C 2) alkoxy radicals, C 1 -C 4 alkyl radicals; optionally substituted with one or more hydroxy, amino, (di) alkylamino, alkoxy, carboxy, sulfonyl radicals; R3 and R4 may also form together with the nitrogen atom to which they are attached a 5- or 7-membered heterocycle whose carbon atoms may be replaced by an optionally substituted oxygen or nitrogen atom; and E at least one coupler chosen from an indoline derivative of formula (II), an indole derivative of formula (III), and one of their addition salts: R '4 R' 40 N 2 In which: R 'represents a hydrogen atom; a linear or branched C 1 -C 10 alkyl radical; a linear or branched C, -C, o (poly) hydroxyalkyl radical; R'2 represents a hydrogen atom; a carboxyl radical; a linear or branched C 1 -C 10 alkyl radical; a linear or branched C 1 -C 0 alkoxycarbonyl radical; R'3 represents a hydrogen atom; a linear or branched C 1 -C 10 alkyl radical; R'4 and R'5 represent, independently of one another, a hydrogen atom; a linear or branched C 1 -C 10 alkyl radical; a linear or branched C 1 -C 10 alkylcarbonyl radical.   2. The composition as claimed in claim 1, in which R 1 and R 2 are chosen from a C 1 -C 6 alkyl radical optionally substituted by a hydroxy, (C 1 -C 2) alkoxy, amino or (di) (C 1 -C 2) alkyl radical. amino; a phenyl, methoxyphenyl, ethoxyphenyl, benzyl radical.   3. The composition of claim 2 wherein R 1 and R 2 are selected from methyl, ethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, phenyl.   4. A composition according to claim 1 wherein R 1 and R 2 together with the nitrogen atoms to which they are attached form a saturated or unsaturated, optionally substituted 5- or 6-membered ring.   5. Composition according to any one of claims 1 and 4 wherein R 1 and R 2 together with the nitrogen atoms to which they are attached form a pyrazolidine ring, pyridazolidine, optionally substituted by one or more C 1 -C 4 alkyl radicals, hydroxy, (C 1 -C 2) alkoxy, carboxy, carboxamido, amino, (di) (C 1 -C 2) alkylamino.   6. A composition according to any one of claims 1 and 4 to 5 wherein R 1 and R 2 together with the nitrogen atoms to which they are attached form a pyrazolidine, pyridazolidine ring.   7. Composition according to any one of the preceding claims wherein R3 and R4 are chosen from a hydrogen atom; a linear or branched C1-C6 alkyl radical optionally substituted by one or more hydroxyl, (C1-C2) alkoxy, amino, (di) (C1-C2) alkylamino radicals; a phenyl radical optionally substituted by one or more hydroxyl, amino, (C 1 -C 2) alkoxy radicals. 10   8. Composition according to any one of claims 1 to 7 wherein R3 and R4 are selected from a hydrogen atom, a methyl, ethyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2 hydroxypropyl, 2-carboxyethyl.   9. Composition according to claim 8 wherein R3 and R4 represent a hydrogen atom.   10. Composition according to any one of claims 1 to 6 wherein R3 and R4 form together with the nitrogen atom to which they are attached a 5- or 7-membered ring selected from heterocycles pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine; said rings may be substituted by one or more hydroxy, amino, (di) (C 1 -C 2) alkylamino, carboxy, carboxamido, C 1 -C 4 alkyl radicals optionally substituted with one or more hydroxy, amino, (di) alkylamino C 1 radicals; C2.   11. A composition according to any one of claims 1 to 6 and wherein R3 and R4 together with the nitrogen atom to which they are attached form a 5- or 7-membered ring selected from pyrrolidine, 2,5- dimethylpyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4-hydroxypyrrolidin-2-carboxylic acid, 2,4-diharboxypyrrolidine, 3-hydroxy-2-hydroxymethyl-pyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-pyrrolidine, 2-hydroxycarboxamidopyrrolidine, 2- (diethylcarboxamido) pyrrolidine, 2-hydroxymethyl pyrrolidine, 3,4-dihydroxy-2-hydroxymethylpyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxypyrrolidine, 3-aminopyrrolidine, 3-methylaminopyrrolidine, 3-dimethylaminopyrrolidine, 4-amino-3-hydroxy pyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) amino-pyrrolidine, piperidine, 2,6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperidine 2-hydroxymethylpiperidine, 3-hydroxy-2-hyd roxymethylpiperidine, 3hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxyhomopiperidine, 2carboxamidohomopiperidine, homopiperazine, N-methyl-homopiperazine, N- (2-hydroxyethyl) homopiperazine.   12. Composition according to any one of claims 1 to 6 and 10 to 11 wherein R3 and R4 together with the nitrogen atom to which they are attached form a 5- or 7-membered ring selected from pyrrolidine; hydroxypyrrolidine, 3-aminopyrrolidine, 3dimethylamino-pyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, piperidine, hydroxypiperidine, homopiperidine, diazepane, N-methylhomopiperazine, N, 3-hydroxyethylhomopiperazine.   13. Composition according to any one of claims 1 to 6 and 10 to 12 wherein R3 and R4 form together with the nitrogen atom to which they are attached a 5-membered ring such as pyrrolidine, 3hydroxypyrrolidine, 3 -aminopyrrolidine, 3-dimethylamino-pyrrolidine.   14. Composition according to claim 1 to 13 wherein the compound of formula (I) or an addition salt thereof is chosen from: 2,3-Diamino-6,7-dihydro-1H, 5H-pyrazolo [1 , 2-a] pyrazol-1-one; 2-Amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3-isopropylamino-6,7dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-Amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one; 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3one; 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one; 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2-amino-3-dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one; 2,3-Diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one 4-amino-1,2-diethyl-5-pyrrolidin-1-yl; 1,2-dihydro-pyrazol-3-one; 4-Amino5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one; 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one.   15. Composition according to any one of the preceding claims, in which R 'is chosen from a hydrogen atom; an alkyl radical.   16. The composition of claim 15 wherein R 'is selected from a hydrogen atom; a methyl radical; an ethyl radical; a propyl radical; a butyl radical.   17. Composition according to any one of the preceding claims wherein R'2 is chosen from a hydrogen atom; a carboxyl radical.   18. Composition according to any one of the preceding claims wherein R'3 is a hydrogen atom.   19. Composition according to any one of the preceding claims wherein R'4 is a hydrogen atom.   20. Composition according to any one of the preceding claims wherein R'5 is a hydrogen atom.   21. Composition according to any one of the preceding claims, in which the indoline derivative (s) of formula (II) are chosen from 5,6-dihydroxyindoline; N-methyl-5,6-dihydroxyindoline; N-ethyl-5,6-dihydroxyindoline; N-propyl-5,6-dihydroxyindoline; N-butyl-5,6-dihydroxyindoline; 5,6-dihydroxyindoline-2-carboxylic acid.   22. Composition according to any one of the preceding claims, in which the indole derivative (s) of formula (III) are chosen from 5,6-dihydroxyindole; N-methyl-5,6-dihydroxyindole; N-ethyl-5,6-dihydroxyindole; N-propyl-5,6-dihydroxyindole; N-butyl-5,6-dihydroxyindole; 5,6-dihydroxyindole-2-carboxylic acid; 2-methyl-6,6-dihydroxyindole; 3-methyl-5,6-dihydroxyindole; 2,3-dimethyl-5,6-dihydroxyindole; 2-ethoxycarbonyl-5,6-dihydroxyindole.   23. Composition according to any one of the preceding claims, comprising an additional oxidation base chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines and bases. heterocyclics different from the derivatives of formula (I) as defined in any one of claims 1 to 14 and their addition salts, and mixtures thereof.   24. Composition according to any one of the preceding claims wherein the amount of each of the oxidation bases is between 0.001 and 10% by weight of the total weight of the dyeing composition.   25. Composition according to any one of the preceding claims, comprising an additional coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers different from the derivatives of formulas (II) and (III) such as defined in any one of claims 1 and 15 to 22 and their addition salts, and mixtures thereof.   26. Composition according to any one of the preceding claims wherein the amount of each of the couplers is between 0.001 and 10% by weight of the total weight of the dye composition.   27. Composition according to any one of the preceding claims further comprising an oxidizing agent.   28. A process for dyeing keratinous fibers, characterized in that a composition as defined in any one of claims 1 to 26 is applied to the keratinous fibers in the presence of an oxidizing agent for a time sufficient to develop the coloration. desired.   29. The method of claim 28 wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.   30. Multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 26 and a second compartment contains an oxidizing agent.   31. Use for the oxidation dyeing of keratin fibers of a composition as defined in any one of claims 1 to 27.