WO2002074267A1 - Novel dyeing compositions for the dyeing of keratin fibres comprising 6-membered heterocyclic hydrazone compounds as an oxidation base - Google Patents

Novel dyeing compositions for the dyeing of keratin fibres comprising 6-membered heterocyclic hydrazone compounds as an oxidation base Download PDF

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Publication number
WO2002074267A1
WO2002074267A1 PCT/FR2002/000856 FR0200856W WO02074267A1 WO 2002074267 A1 WO2002074267 A1 WO 2002074267A1 FR 0200856 W FR0200856 W FR 0200856W WO 02074267 A1 WO02074267 A1 WO 02074267A1
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radical
methyl
hydrazone
ylidene
amino
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PCT/FR2002/000856
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French (fr)
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Laurent Vidal
Hervé David
Véronique Birault
Eric Terranova
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L'oreal
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Publication of WO2002074267A1 publication Critical patent/WO2002074267A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/20—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms

Definitions

  • the subject of the invention is a new dye composition useful for the
  • oxidation bases such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds.
  • oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise to colored compounds by an oxidative condensation process.
  • couplers or color modifiers the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as than
  • the dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which is generally sensitized differently (ie damaged) between its tip and its root.
  • the object of the present invention is to provide compositions for the dyeing of keratin fibers by oxidation which have powerful bright dyes, not very selective and particularly resistant, capable of generating intense colorings in various shades.
  • - A represents a hydrogen atom; an acyl radical, an O ⁇ 4 alkylsulfonyl radical or an arylsulfonyl radical, these radicals being optionally substituted by a methyl, a C ⁇ Cz alkoxy or a carboxyl,
  • R. represents a carbon chain in C ⁇ -C, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may form a ring having 3 to 6 members, optionally aromatic, one or several carbon atoms in the chain which can be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group with the exception of carbon linked to the nitrogen atom; the radical R 1 comprising no peroxide bond, nor diazo, nitro or nitroso radicals;
  • R 2 , R 3 , R 4 and R 5 each represent a hydrogen atom separately; a linear or branched CpC ⁇ 2 alkyl or alkenyl radical or in the form of a carbon ring having 3 to 6 members, optionally aromatic; one or more carbon atoms of the alkyl or alkenyl radicals which can be replaced by one or more oxygen, nitrogen or sulfur atoms, by an SO 2 group, with the following conditions
  • radicals or alkyl groups are linear or branched and contain from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
  • An alkoxy is O-alkyl in which the term alkyl is as defined above.
  • An alkylsulfonyl radical is an Alk-SO 2 - radical
  • an arylsulfonyl radical is an Ar-SO 2 - radical
  • an alkylsulfoxide radical is an Alk-SO- radical
  • an arylsulfoxide radical is an Ar-SO- radical.
  • An aryl radical is for example a phenyl or naphthyl group, preferably phenyl.
  • the object of the present invention relates to compositions containing one and / or the other of the tautomeric forms of formulas (I) and (F).
  • the following will be limited to the description of compounds of formula (I), this teaching being directly transposable to the compounds of formula (F).
  • the radical R 1 when it is indicated that one or more of the carbon atoms of the radical R 1 can be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group, and / or that> said radical R., can contain one or more double bonds, this means that one can, for example, make the following transformations: i - CH - H can become I ° -H
  • radicals R 1 chosen from a C 1 -C 4 alkyl or alkenyl radical which may be substituted by one or more hydroxy, optionally substituted amino or carboxyl substituents are preferred; a phenyl radical which may be substituted by one or more halogen atoms, one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy amino, hydroxy, trifluoromethyl, alkylamino C 1 -C 4 , carboxyl, sulfonyl; a benzyl radical which may be substituted by a halogen atom, one or more C r C 4 alkyl, O, O 4 alkoxy, amino, trifluoromethyl groups; a C 1 -C 4 alkylamino radical; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) p -T- (CH2) q -VR 'where p
  • the methyl radicals are more particularly preferred; ethyl; isopropyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; 2-methoxyphenyl; 3- methoxyphenyl; 4-methoxyphenyl; 2-hydroxyphenyl; 3-hydroxyphenyl; 4- hydroxyphenyl; benzyl; heterocycles chosen from pyridyle, imidazolyle, pyrimidinyle. More particularly, the radicals R, methyl are preferred; ethyl; phenyl; 2-methoxyphenyl; 2-hydroxyphenyl, hydroxyethle, aminoethyl, carboxyethyl.
  • R 2 , R 3 , R 4 and R 5 are chosen from a hydrogen atom; an alkyl radical, for example methyl, ethyl, propyl, isopropyl; an alkyl radical substituted by a hydroxy, amino or a halogen such as hydroxymethyl, hydroxyethyl, 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, aminoethyl, aminopropyl trifluoromethyl; a phenyl radical which may be substituted by one or more substituents chosen from alkyl, hydroxy, amino, alkoxy, carboxy, trifluoromethyl, sulfonic radicals
  • the preferred radicals R 2 , R 3 , R 4 and R 5 are hydrogen; an alkyl radical chosen from methyl, ethyl; a substituted alkyl radical chosen from trifluoromethyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; benzyl; a phenyl optionally substituted by one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; 2-methoxybenzyl; 4-methoxybenzyl; 2- hydroxy benzyl; 4-hydroxybenzyl; a heterocycle chosen from pyrrolidinyl, piperidinyl; a methoxy radical; an acyl radical; an amino radical. More particularly, the radicals R 2, R 3 , R 4 and R 5 are chosen from hydrogen; methyl; ethyl; trifluoromethyl; phenyl; pyrrolidinyl; methoxy; amino.
  • radicals A of the formula (I) defined above the radicals chosen from hydrogen are preferred; an acyl radical; a methylsulfonyl radical; a phenyisulfonyl radical; a toluylsulfonyl radical. More particularly, the radical A is hydrogen.
  • the compound of formula (I) has one of the following formulas:
  • R. ,, R 2 , R 3 , R 4 , R 5 and A are as defined above.
  • compounds of formula (la) called (2-R1-2H- pyridazin-3-ylidene) hydrazones, there may be mentioned
  • N-methanesulfonic acid (2-Methyl ⁇ 2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (2-hydroxyethyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (2- (2-amino-ethyl) -2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (6-pyrrolidino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (5-a
  • N-phenyIsulfonic acid (2-Methyl-2H-pyridazin-3-ylidene) -hydrazone; N-N-phenylsulfonic acid (2-hydroxyethyl-2H-pyridazin-3-ylidene) -hydrazone; N-phenysulfonic acid (2- (2-amino-ethyl) -2H-pyridazin-3-ylidene) -hydrazone; N-phenylsulfonic acid (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-phenylsulfonic acid (6-pyrrolidino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; ; N-phenylsulfonic acid (6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; ; N-phenylsulfonic acid
  • N- R1-2H- pyrazin-3-ylidene azone
  • N-Methyl-2H-pyrazin-2-ylidene-hydrazone N-hydroxyethyl-2H-pyrazin-2-ylidene-hydrazone
  • N- (2-amino-ethyl) -2H-pyrazin-2-ylidene-hydrazone N- (2-amino-ethyl) -2H-pyrazin-2-ylidene-hydrazone
  • 3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene-hydrazone 3-phenyl-N-methyl-2H-pyrazin-2-ylidene-hydrazone.
  • N-methanesulfonic acid N-Methyl-2H-pyrazin-2-ylidene -hydrazone; N-methanesulfonic acid (N-hydroxyethyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (N- (2-amino-ethyl) -2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-methoxy-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-phenyl-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-amino-N-methyl-2H,
  • N-phenyIsulfonic acid N-Methyl-2H-pyrazin-2-ylidene -hydrazone; N-phenylsulfonic acid (N-hydroxyethyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (N- (2-amino-ethyl) -2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-methoxy-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-phenyl-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-amino-N-methyl-2H-pyr
  • N-methanesulfonic acid N-Methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (N-hydroxyethyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (N- (2-amino-ethyl) -2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (4-methoxy-N-methyl-2H-pyrimidin-2-ylidene) - hydrazone; ; N-methanesulfonic acid (4,6-dimethoxy-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (4-pyrrolidino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (4-phenyl)
  • N-N-phenylsulfonic acid N-hydroxyethyl-2H-pyrimidin-2-ylidene) -hydrazone; N-phenylsulfonic acid (N- (2-amino-ethyl) -2H-pyrimidin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-methoxy-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-pheny-sulfonic acid (3-pyrrolidino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-phenyl-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-phenysulfonic acid (3-amino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone.
  • N-methanesulfonic acid (3-Methyl-2H-pyrimidin-4-ylidene) -hydrazone
  • N-methanesulfonic acid (3-hydroxyethyl-2H-pyrimidin-4-ylidene) -hydrazone
  • N-methanesulfonic (3- (2-amino-ethyl) -2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-methoxy-2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-pyrrolidino-2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-phenyl-2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-amino-2H-pyrimidin-4-ylidene) -hydrazone.
  • N-phenyIsulfonic acid (3-Methyl-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-hydroxyethyl-2H-pyrimidin-4-ylidene) -hydrazone; N- acid phenylsulfonic (3- (2-amino-ethyl) -2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-methoxy-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-pyrrolidino-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-phenyl-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-amino-2H-pyrimidin-4-
  • the hydrazone type oxidation base corresponds to the following formula:
  • the hydrazone compound is chosen from 6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone, 6- (pyrrolidin-N- yl) -2-methyl-2H-pyridazin-3- ylidene) -hydrazone, 6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone.
  • the coupler useful in the composition of the present invention is a coupler conventionally used for dyeing keratin fibers.
  • couplers mention may in particular be made of metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers.
  • heterocyclic couplers which can be used in the dye composition in accordance with the invention, mention may in particular be made of indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyrazolo-azole derivatives, derivatives pyrroloazoles, imidazolo-azole derivatives, pyrazolo-pyrimidine derivatives, pyrazolin-3,5-diones derivatives, pyrrolo- [3,2-d] -oxazole derivatives, pyrazolo- [3,4- derivatives d] -thiazolics, the S-oxide-thiazolo-azolic derivatives, the S, S-dioxide-thiazolo-azolic derivatives, and their addition salts with an acid.
  • the compound or compounds of formula (I) are each preferably present in an amount of between 0.001 and 10%, more preferably between 0.005 and 6% by weight of the total weight of the dye composition and the or the couplers are present in an amount preferably of between 0.001 and 10%, more preferably from 0.005 to 6% by weight of the total weight of the dye composition.
  • composition according to the present invention may also comprise one or more additional oxidation bases different from the oxidation bases of formula (I).
  • additional oxidation bases are chosen from the oxidation bases conventionally used in oxidation dyeing, for example paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
  • paraphenylenediamines there may be mentioned by way of example, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N- bis- ( ⁇ - hydroxyethyl) paraphenylenediamine, 4-N, N-bis- ( ⁇ -hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- ( ⁇ -hydroxyethyl) amino 2-chloro aniline, 2- ⁇ -hydroxyethyl paraphenyl
  • paraphenylenediamine paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2- ⁇ -hydroxyethyl paraphenylenediamine, 2- ⁇ -hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- ( ⁇ -hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2- ⁇ -acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred .
  • the bis-phenylalkylenediamines there may be mentioned by way of example, N, N'-bis- ( ⁇ -hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N , N'-bis- ( ⁇ -hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( ⁇ -hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1, 8-bis- (2,
  • para-aminophenol there may be mentioned by way of example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
  • para-aminophenol 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
  • ortho-aminophenols there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.
  • heterocyclic bases for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
  • pyridine derivatives mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- ( ⁇ -methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.
  • pyrimidine derivatives mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned 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
  • the additional base is present in an amount preferably between 0.001 and 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 6
  • the addition salts with an acid which can be used in the context of the dye compositions of the invention for the oxidation bases and the couplers are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • the addition salts which can be used in the context of the invention are for example chosen from addition salts with sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • the dye composition in accordance with the invention may also contain one or more direct dyes which can in particular be chosen from nitro dyes of the benzene series, cationic direct dyes, azo direct dyes, methinic direct dyes.
  • the medium suitable for dyeing also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water.
  • organic solvent mention may, for example, be made of lower C r C 4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents may be 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 the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, agents mineral or organic thickeners, and in particular associative anionic, cationic, nonionic and amphoteric polymeric thickeners, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
  • adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, nonionic, amphoteric
  • adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.
  • the pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.
  • acidifying agents there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
  • mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
  • basifying agents there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below:
  • the dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
  • the invention also relates to a process for dyeing keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above.
  • the composition according to the present invention as defined above is applied to the fibers, the color being revealed using an oxidizing agent.
  • the color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied simultaneously or sequentially to the composition of the invention on the fibers.
  • 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 enough to develop color.
  • the mixture obtained is then applied to the keratin fibers. After an exposure time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin 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 bramates, persalts such as perborates and persulfates, peracids and d systems. 'enzymatic oxidations.
  • the enzymatic oxidation systems are for example chosen from peroxidases, where appropriate in the presence of at least one donor for these peroxidases, oxidoreductases with 2 electrons in the presence of at least one donor for these oxidoreductases, and oxidoreductases with 4 electrons.
  • the oxidizing composition containing the oxidizing agent may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
  • the pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 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 in dyeing keratin fibers and as defined above.
  • composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.
  • Another object of the invention is a device with several compartments or "kit” for dyeing in which a first compartment contains the dye composition defined above and a second compartment contains the oxidizing composition.
  • This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.
  • a subject of the invention is also the colored product resulting from the reaction of at least one compound of formula (I) as defined above with a coupler in the presence of at least one oxidizing agent as defined above.
  • These colored products may in particular be in the form of pigments and be used as direct dye for the direct dyeing of the hair or even be incorporated in cosmetic products such as for example in makeup products.
  • the present invention finally relates to new compounds of formulas (I), (la), (Ib), (le) as defined above.
  • the examples which follow serve to illustrate the invention without however limiting its scope.
  • Step 1 Preparation of the 2-methyl-3-chloro-6-methoxypyridazinium methosulfate salt
  • Step 2 Preparation of N-acetyl (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone.
  • each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight).
  • Example 1 (1) prepared according to the synthesis of Example 1 from 3-chloro 6-pyrrolidin-N-yl-pyridazine; (2) prepared according to the synthesis of Example 1 from 3-chloro 6-phenylpyrazine.
  • each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight).
  • a final pH of 7 is obtained with the dye support (2) and a pH 9.5 with the dye support (1).
  • Each mixture obtained is applied to locks of gray hair containing 90% white hairs. After 30 min of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

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Abstract

The invention relates to a novel composition that is used for the oxidation dyeing of keratin fibres, in particular human hair, comprising at least one particular hydrazone-type compound as an oxidation base and at least one coupling agent. The invention also relates to the method using same and to novel 6-membered heterocyclic hydrazone compounds.

Description

COMPOSITIONS TINCTORIALES POUR LA TEINTURE DE FIBRES KERATINIQUES COMPRENANT A TITRE DE BASE D ' OXYDATION DES COMPOSES HYDRAZONE HETEROCYCLIQUES A 6 CHAINONSTINCTORIAL COMPOSITIONS FOR DYEING KERATINIC FIBERS COMPRISING THE OXIDATION BASE OF 6-CHAIN HETEROCYCLIC HYDRAZONE COMPOUNDS
L'invention a pour objet une nouvelle composition tinctoriale utile pour laThe subject of the invention is a new dye composition useful for the
5 teinture par oxydation des fibres kératiniques, en particulier des cheveux humains comprenant à titre de base d'oxydation au moins un composé particulier du type hydrazone ainsi que le procédé de teinture les mettant en œuvre. L'invention a aussi pour objet de nouveaux composés hydrazone.5 dyeing by oxidation of keratinous fibers, in particular human hair comprising as oxidation base at least one particular compound of the hydrazone type as well as the dyeing process using them. The subject of the invention is also new hydrazone compounds.
Il est connu de teindre les fibres kératiniques et en particulier les cheveux 10 humains avec des compositions tinctoriales contenant des précurseurs de colorant d'oxydation, appelés généralement bases d'oxydation, tels que des ortho ou paraphénylènediamines, des ortho ou paraaminophénols et des composés hétérocycliques. Ces bases d'oxydation sont des composés incolores ou faiblement colorés qui, associés à des produits oxydants, peuvent donner naissance par un 15 processus de condensation oxydative à des composés colorés.It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds. . These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise to colored compounds by an oxidative condensation process.
On sait également que l'on peut faire varier les nuances obtenues avec ces bases d'oxydation en les associant à des coupleurs ou modificateurs de coloration, ces derniers étant choisis notamment parmi les métadiamines aromatiques, les métaaminophénols, les métadiphénols et certains composés hétérocycliques tels queWe also know that we can vary the nuances obtained with these oxidation bases by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as than
20 des composés indoliques.20 indole compounds.
La variété des molécules mises en jeu au niveau des bases d'oxydation et des coupleurs, permet l'obtention d'une riche palette de couleurs.The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.
La coloration dite "permanente" obtenue grâce à ces colorants d'oxydation, doit par ailleurs satisfaire un certain nombre d'exigences. Ainsi, elle doit être sans 25 inconvénient sur le plan toxicologique, elle doit permettre d'obtenir des nuances dans l'intensité souhaitée et présenter une bonne tenue face aux agents extérieurs tels que la lumière, les intempéries, le lavage, les ondulations permanentes, la transpiration et les frottements.The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and exhibit good resistance to external agents such as light, bad weather, washing, permanent undulations, perspiration and friction.
Les colorants doivent également permettre de couvrir les cheveux blancs, 30 et être enfin les moins sélectifs possibles, c'est-à-dire permettre d'obtenir des écarts de coloration les plus faibles possibles tout au long d'une même fibre kératinique, qui est en général différemment sensibilisée (i.e. abîmée) entre sa pointe et sa racine.The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which is generally sensitized differently (ie damaged) between its tip and its root.
Il est déjà connu d'utiliser des composés hydrazones en particulier pour la réalisation de composition pour la teinture de fibres kératiniques. Par exemple, laIt is already known to use hydrazone compounds in particular for the preparation of a composition for dyeing keratin fibers. For example, the
35 demande de brevet FR1599968 au nom de THERACHEMIE et la demande de brevet DE1922400 au nom de HENKEL décrivent de telles compositions. Ces compositions ne sont cependant pas totalement satisfaisantes, en particulier, elles ne sont pas totalement satisfaisantes au niveau de la brillance et de la puissance de la couleur obtenue. Le but de la présente invention est de fournir de nouvelles compositions tinctoriales ne présentant pas les inconvénients de celles de la technique antérieure.35 patent application FR1599968 in the name of THERACHEMIE and the patent application DE1922400 in the name of HENKEL describe such compositions. These compositions are not, however, completely satisfactory, in particular, they are not completely satisfactory in terms of the gloss and the power of the color obtained. The object of the present invention is to provide new dye compositions which do not have the drawbacks of those of the prior art.
En particulier, le but de la présente invention est de fournir des compositions pour la teinture de fibres kératiniques par oxydation qui présentent des teintures brillantes puissantes, peu sélectives et particulièrement résistantes, capables d'engendrer des colorations intenses dans des nuances variées.In particular, the object of the present invention is to provide compositions for the dyeing of keratin fibers by oxidation which have powerful bright dyes, not very selective and particularly resistant, capable of generating intense colorings in various shades.
Ce but est atteint avec la présente invention qui a pour objet une composition tinctoriale pour la teinture de fibres kératiniques comprenant dans un milieu approprié pour la teinture de ces fibres,This object is achieved with the present invention which relates to a dye composition for dyeing keratin fibers comprising, in a medium suitable for dyeing these fibers,
• à titre de base d'oxydation, au moins un composé du type hydrazone de formule (I) suivante ou le sel d'addition avec un acide ou une base correspondant• as oxidation base, at least one compound of the hydrazone type of formula (I) below or the addition salt with a corresponding acid or base
Figure imgf000003_0001
dans laquelle
Figure imgf000003_0001
in which
- X représente un atome d'azote ou CR2 ; Y représente un atome d'azote ou CR3 ; Z représente un atome d'azote ou CR4 et W représente un atome d'azote ou CR5 ;- X represents a nitrogen atom or CR2; Y represents a nitrogen atom or CR3; Z represents a nitrogen atom or CR4 and W represents a nitrogen atom or CR 5 ;
- A représente un atome d'hydrogène ; un radical acyle , un radical alkylsulfonyle en 0^4 ou un radical arylsulfonyle, ces radicaux étant éventuellement substitués par un méthyl, un alkoxy en C^Cz ou un carboxyl,- A represents a hydrogen atom; an acyl radical, an O ^ 4 alkylsulfonyl radical or an arylsulfonyl radical, these radicals being optionally substituted by a methyl, a C ^ Cz alkoxy or a carboxyl,
- R., représente une chaîne carbonée en Cι-C , saturée ou pouvant contenir une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples, linéaire ou ramifiée pouvant former un cycle ayant de 3 à 6 chaînons, éventuellement aromatique, un ou plusieurs atomes de carbone de la chaîne pouvant être remplacés par un atome d'oxygène, d'azote, d'halogène ou de soufre ou par un groupe SO2 à l'exception du carbone lié à l'atome d'azote; le radical R1 ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;- R., represents a carbon chain in Cι-C, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may form a ring having 3 to 6 members, optionally aromatic, one or several carbon atoms in the chain which can be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group with the exception of carbon linked to the nitrogen atom; the radical R 1 comprising no peroxide bond, nor diazo, nitro or nitroso radicals;
- R2, R3, R4 et R5 représentent, chacun séparément un atome d'hydrogène ; un radical alkyle ou alcényle en CpCι2, linéaire ou ramifié ou sous forme de cycle carboné ayant de 3 à 6 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone des radicaux alkyle ou alcényle pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote ou de soufre, par un groupement SO2, avec les conditions suivantes- R 2 , R 3 , R 4 and R 5 each represent a hydrogen atom separately; a linear or branched CpCι 2 alkyl or alkenyl radical or in the form of a carbon ring having 3 to 6 members, optionally aromatic; one or more carbon atoms of the alkyl or alkenyl radicals which can be replaced by one or more oxygen, nitrogen or sulfur atoms, by an SO 2 group, with the following conditions
- un des groupes X, Y, W et Z représente un atome d'azote, - lorsque X = N, alors Y = CR3 et Z = CR4 et W = CR5,- one of the groups X, Y, W and Z represents a nitrogen atom, - when X = N, then Y = CR 3 and Z = CR 4 and W = CR 5 ,
- lorsque Z = N, alors X = CR2 et Y = CR3 et W = CR5,- when Z = N, then X = CR 2 and Y = CR 3 and W = CR 5 ,
- lorsque W = N, alors X = CR2 et Y - CR3 et Z = CR4, ou- when W = N, then X = CR 2 and Y - CR 3 and Z = CR 4 , or
- lorsque Y = N, alors X = CR2 et Z = CR4 et W = CR5 et avec les conditions supplémentaires suivantes : si X = N, Y = CR3, Z = CR4 et W = CR5, alors le groupe R4 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde , si Z = N, X = CR2, Y = CR3 et W = CR5, alors le groupe R2 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde, si W = N, X = CR2, Y = CR3 et Z = CR4, alors le groupe R3 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde, si Y = N, X = CR2, Z = CR4 et W = CR5, alors le groupe R5 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde, et • au moins un coupleur ou le sel d'addition avec un acide correspondant.- when Y = N, then X = CR 2 and Z = CR 4 and W = CR 5 and with the following additional conditions: if X = N, Y = CR 3 , Z = CR 4 and W = CR 5 , then the group R 4 is different from an alkylsulfonyl, arylsulfonyl, alkylsulfoxide or arylsulfoxide radical, if Z = N, X = CR 2 , Y = CR 3 and W = CR 5 , then the R 2 group is different from an alkylsulfonyl radical, arylsulfonyl, alkylsulfoxide or arylsulfoxide, if W = N, X = CR 2 , Y = CR 3 and Z = CR 4 , then the group R 3 is different from an alkylsulfonyl, arylsulfonyl, alkylsulfoxide or arylsulfoxide radical, if Y = N, X = CR 2 , Z = CR 4 and W = CR 5 , then the group R 5 is different from an alkylsulfonyl, arylsulfonyl, alkylsulfoxide or arylsulfoxide radical, and • at least one coupler or the addition salt with a corresponding acid .
Dans les définitions ci-dessus, sauf autre indication, les radicaux ou groupes alkyle sont linéaires ou ramifiés et comprennent de 1 à 10 atomes de carbone, de préférence 1 à 4 atomes de carbone. Un alcoxy est O-alkyle dans lequel le terme alkyle est tel que défini précédemment.In the above definitions, unless otherwise indicated, the radicals or alkyl groups are linear or branched and contain from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. An alkoxy is O-alkyl in which the term alkyl is as defined above.
Un radical alkylsulfonyle est un radical Alk-SO2-, un radical arylsulfonyle est un radical Ar-SO2-, un radical alkylsulfoxyde est un radical Alk-SO-, un radical arylsulfoxyde est un radical Ar-SO-.An alkylsulfonyl radical is an Alk-SO 2 - radical, an arylsulfonyl radical is an Ar-SO 2 - radical, an alkylsulfoxide radical is an Alk-SO- radical, an arylsulfoxide radical is an Ar-SO- radical.
Un radical aryle est par exemple un groupe phényle ou naphtyle, de préférence phényle. Selon le pH de la composition, il peut exister dans le milieu un équilibre acido-basique entre la formule (I) et la formule (F) ci-dessous.An aryl radical is for example a phenyl or naphthyl group, preferably phenyl. Depending on the pH of the composition, there may exist in the medium an acid-base balance between formula (I) and formula (F) below.
Figure imgf000005_0001
Figure imgf000005_0001
(D (i)(D (i)
L'objet de la présente invention porte sur les compositions contenant l'une et/ou l'autre des formes tautomères de formules (I) et (F). Cependant, par souci de clarté, on se limitera dans ce qui suit à la description de composés de formule (I), cet enseignement étant directement transposable aux composés de formule (F). Selon l'invention, lorsqu'il est indiqué qu'un ou plusieurs des atomes de carbone du radical R1 peuvent être remplacés par un atome d'oxygène, d'azote, d'halogène ou de soufre ou par un groupement SO2, et/ou que> ledit radical R., peut contenir une ou plusieurs liaisons doubles, cela signifie que l'on peut, à titre d'exemple, faire les transformations suivantes : i — CH — H peut devenir I °-HThe object of the present invention relates to compositions containing one and / or the other of the tautomeric forms of formulas (I) and (F). However, for the sake of clarity, the following will be limited to the description of compounds of formula (I), this teaching being directly transposable to the compounds of formula (F). According to the invention, when it is indicated that one or more of the carbon atoms of the radical R 1 can be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group, and / or that> said radical R., can contain one or more double bonds, this means that one can, for example, make the following transformations: i - CH - H can become I ° -H
Figure imgf000005_0002
Figure imgf000005_0002
Parmi les radicaux R1 définie ci-dessus, on préfère les radicaux choisis parmi un radical alkyle ou alcényle en CrC4 pouvant être substitué par un ou plusieurs substituants hydroxy, amino éventuellement substitué, carboxyl ; un radical phényle pouvant être substitué par un ou plusieurs atomes d'halogène, un ou plusieurs groupes alkyle en C|-C4, alcoxy en C^C^ amino, hydroxy, trifluorométhyle, alkylamino en C1-C4, carboxyl, sulfonyle ; un radical benzyle pouvant être substitué par un atome d'halogène, un ou plusieurs groupes alkyle en CrC4, alcoxy en 0,-04, amino, trifluorométhyle ; un radical alkylamino en C1-C4 ; un hétérocycle choisi parmi imidazole, le thiazole, la pyridine ou la pyrimidine ; un radical (CH2)p-T-(CH2)q-VR' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle.Among the radicals R 1 defined above, the radicals chosen from a C 1 -C 4 alkyl or alkenyl radical which may be substituted by one or more hydroxy, optionally substituted amino or carboxyl substituents are preferred; a phenyl radical which may be substituted by one or more halogen atoms, one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy amino, hydroxy, trifluoromethyl, alkylamino C 1 -C 4 , carboxyl, sulfonyl; a benzyl radical which may be substituted by a halogen atom, one or more C r C 4 alkyl, O, O 4 alkoxy, amino, trifluoromethyl groups; a C 1 -C 4 alkylamino radical; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) p -T- (CH2) q -VR 'where p and q are whole, identical or different, comprised between 1 and 3, R' represents H or methyl and T and V independently denote an oxygen atom or a radical NR "with R" denoting hydrogen or methyl.
Parmi les radicaux R., de la formule (I) définie ci-dessus, on préfère plus particulièrement les radicaux méthyle ; éthyle ; isopropyle ; hydroxyéthyle ; aminoéthyle ; carboxyméthyle ; carboxyéthyle ; phényle ; 2-méthoxyphényle ; 3- méthoxyphényle ; 4-méthoxyphényle ; 2-hydroxyphényle ; 3-hydroxyphényle ; 4- hydroxyphényle ; benzyle ; les hétérocycles choisis parmi pyridyle, imidazolyle, pyrimidinyle. Plus particulièrement, on préfère les radicaux R, méthyle ; éthyle ; phényle ; 2-méthoxyphényl ; 2-hydroxyphényl, hydroxyéthle, aminoéthyle, carboxyéthyle.Among the radicals R., of the formula (I) defined above, the methyl radicals are more particularly preferred; ethyl; isopropyl; hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; 2-methoxyphenyl; 3- methoxyphenyl; 4-methoxyphenyl; 2-hydroxyphenyl; 3-hydroxyphenyl; 4- hydroxyphenyl; benzyl; heterocycles chosen from pyridyle, imidazolyle, pyrimidinyle. More particularly, the radicals R, methyl are preferred; ethyl; phenyl; 2-methoxyphenyl; 2-hydroxyphenyl, hydroxyethle, aminoethyl, carboxyethyl.
Lorsqu'il est indiqué pour R2, R3, R4 et R5 qu'un ou plusieurs des atomes les constituants peuvent être remplacés par un atome d'oxygène, d'azote, ou de soufre ou par un groupement SO2, cela signifie que l'on peut faire les transformations décrites précédemment pour R Les radicaux R2, R3, R4 et R5, de la formule (I) préférés sont choisis parmi un atome d'hydrogène ; un radical alkyle par exemple méthyle, éthyle, propyle, isopropyle ; un radical alkyle substitué par un hydroxy, amino ou un halogène comme hydroxyméthyle, hydroxyéthyle, 1 ,2-dihydroxyéthyle, 1 ,2-dihydroxypropyle, 2,3- dihydroxypropyle, aminométhyle, aminoéthyle, aminopropyle trifluorométhyle ; un radical phényle pouvant être substitué par un ou plusieurs substituants choisis parmi les radicaux alkyle, hydroxy, amino, alcoxy, carboxy, trifluorométhyle, sulfonique ; les radicaux benzyle et les benzyles substitués par un alcoxy, par exemple méthoxy, ou hydroxy notamment 2-méthoxybenzyle, 3-méthoxybenzyle, 4-méthoxybenzyle, 2- hydroxybenzyle, 3-hydroxybenzyle, 4-hydroxybenzyle ; un hétérocycle choisi parmi N- pyrrolidinyle, N-pipéridinyle, N-morpholine, N-pipérazinyle ou N-imidazolyle ; un radical alcoxy comme méthoxy ou éthoxy ; un radical phosphonyle ; un radical siloxy ; un radical amino ; un radical acyle ; un radical acylamino ; un radical sulfonamide ; un radical uréido ; un radical sulfonylamino.When it is indicated for R 2 , R 3 , R 4 and R 5 that one or more of the atoms of the constituents can be replaced by an oxygen, nitrogen, or sulfur atom or by an SO 2 group, this means that the transformations described above can be done for R The preferred radicals R 2 , R 3 , R 4 and R 5 , of formula (I) are chosen from a hydrogen atom; an alkyl radical, for example methyl, ethyl, propyl, isopropyl; an alkyl radical substituted by a hydroxy, amino or a halogen such as hydroxymethyl, hydroxyethyl, 1,2-dihydroxyethyl, 1,2-dihydroxypropyl, 2,3-dihydroxypropyl, aminomethyl, aminoethyl, aminopropyl trifluoromethyl; a phenyl radical which may be substituted by one or more substituents chosen from alkyl, hydroxy, amino, alkoxy, carboxy, trifluoromethyl, sulfonic radicals; benzyl radicals and benzyls substituted by an alkoxy, for example methoxy, or hydroxy, in particular 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-hydroxybenzyl, 3-hydroxybenzyl, 4-hydroxybenzyl; a heterocycle chosen from N-pyrrolidinyl, N-piperidinyl, N-morpholine, N-piperazinyl or N-imidazolyl; an alkoxy radical such as methoxy or ethoxy; a phosphonyl radical; a siloxy radical; a amino radical; an acyl radical; an acylamino radical; a sulfonamide radical; a ureido radical; a sulfonylamino radical.
Les radicaux R2, R3, R4 et R5 préférés sont l'hydrogène ; un radical alkyle choisi parmi méthyle, éthyle ; un radical alkyle substitué choisi parmi trifluorométhyle; hydroxyméthyle, hydroxyéthyle, aminométhyle, aminoéthyle ; le benzyle ; un phényl éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux méthyle, hydroxy, amino, méthoxy ; 2-méthoxybenzyle ; 4-méthoxybenzyle ; 2- hydroxy benzyle ; 4-hydroxybenzyle ; un hétérocycle choisi parmi pyrrolidinyle, pipéridinyle ; un radical méthoxy ; un radical acyle ; un radical amino. Plus particulièrement, les radicaux R2, R3, R4 et R5 sont choisis parmi l'hydrogène ; méthyle ; éthyle ; trifluorométhyle ; phényle ; pyrrolidinyle ; méthoxy ; amino.The preferred radicals R 2 , R 3 , R 4 and R 5 are hydrogen; an alkyl radical chosen from methyl, ethyl; a substituted alkyl radical chosen from trifluoromethyl; hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; benzyl; a phenyl optionally substituted by one or more radicals chosen from methyl, hydroxy, amino and methoxy radicals; 2-methoxybenzyl; 4-methoxybenzyl; 2- hydroxy benzyl; 4-hydroxybenzyl; a heterocycle chosen from pyrrolidinyl, piperidinyl; a methoxy radical; an acyl radical; an amino radical. More particularly, the radicals R 2, R 3 , R 4 and R 5 are chosen from hydrogen; methyl; ethyl; trifluoromethyl; phenyl; pyrrolidinyl; methoxy; amino.
Parmi les radicaux A de la formule (I) définie ci-dessus, on préfère les radicaux choisis parmi l'hydrogène ; un radical acyle ; un radical méthylsulfonyle ; un radical phényisulfonyle ; un radical toluylsulfonyle. Plus particulièrement, le radical A est l'hydrogène.Among the radicals A of the formula (I) defined above, the radicals chosen from hydrogen are preferred; an acyl radical; a methylsulfonyl radical; a phenyisulfonyl radical; a toluylsulfonyl radical. More particularly, the radical A is hydrogen.
Selon des modes de réalisation particuliers, le composé de formule (I) présente l'une des formules suivantes :According to particular embodiments, the compound of formula (I) has one of the following formulas:
Figure imgf000007_0001
dans lesquelles R.,, R2, R3, R4, R5 et A sont tels que définis précédemment. A titre d'exemple de composés de formule (la), appelés (2-R1-2H- pyridazin-3-ylidene)hydrazones, on peut citer
Figure imgf000007_0001
in which R. ,, R 2 , R 3 , R 4 , R 5 and A are as defined above. By way of example of compounds of formula (la), called (2-R1-2H- pyridazin-3-ylidene) hydrazones, there may be mentioned
• 2-Methyl-2H-pyridazin-3-ylidene hydrazone ; 2-hydroxyethyl-2H-pyridazin- 3-ylidene-hydrazone ; 2-(2-amino-ethyl)-2H-pyridazin-3-ylidene-hydrazone ; 6- méthoχy-2-méthyl-2H- pyridazin-3-ylidene-hydrazone ; 6-pyrrolidino-2-méthyl-2H- pyridazin-3-ylidene-hydrazone ; 6-phényl-2-méthyl-2H-pyridazin-3-ylidene-hydrazone ; 5-amino-2-méthyl-2H-pyridazin-3-ylidene-hydrazone.• 2-Methyl-2H-pyridazin-3-ylidene hydrazone; 2-hydroxyethyl-2H-pyridazin-3-ylidene-hydrazone; 2- (2-amino-ethyl) -2H-pyridazin-3-ylidene-hydrazone; 6 methoχy-2-methyl-2H-pyridazin-3-ylidene-hydrazone; 6-pyrrolidino-2-methyl-2H-pyridazin-3-ylidene-hydrazone; 6-phenyl-2-methyl-2H-pyridazin-3-ylidene-hydrazone; 5-amino-2-methyl-2H-pyridazin-3-ylidene-hydrazone.
• N-acetyl (2-Methyl-2H-pyridazin-3-ylidene)-hydrazone ; N-acetyl (2- hydroxyethyl-2H- pyridazin-3-ylidene)-hydrazone ; N-acetyl (2-(2-amino~ethyl)-2H- pyridazin-3-ylidene)-hydrazone ; N-acetyl (6-méthoxy-2-méthyl-2H- pyridazin-3- ylidene)-hydrazone ; N-acetyl (6-pyrrolidino-2-méthyl-2H- pyridazin-3-ylidene)- hydrazone ; N-acetyl (6-phényl-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone ; N-acetyl (5-amino-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone • N-formyl (2-Methyl-2H-pyridazin-3-ylidene)-hydrazone ; N-formyl (2- hydroxyethyl-2H-pyridazin-3-ylidene)-hydrazone ; N-formyl (2-(2-amino-ethyl)-2H- pyridazin-3-ylidene)-hydrazone ; N-formyl (6-méthoxy-2-méthyl-2H- pyridazin-3- ylidene)-hydrazone ; N-formyl (6-pyrrolidino-2-méthyl-2H- pyridazin-3-ylidene)- hydrazone ; N-formyl (6-phényl-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone ; N-formyl (5-amino-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone• N-acetyl (2-Methyl-2H-pyridazin-3-ylidene) -hydrazone; N-acetyl (2-hydroxyethyl-2H-pyridazin-3-ylidene) -hydrazone; N-acetyl (2- (2-amino ~ ethyl) -2H-pyridazin-3-ylidene) -hydrazone; N-acetyl (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-acetyl (6-pyrrolidino-2-methyl-2H-pyridazin-3-ylidene) - hydrazone; N-acetyl (6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-acetyl (5-amino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone • N-formyl (2-Methyl-2H-pyridazin-3-ylidene) -hydrazone; N-formyl (2-hydroxyethyl-2H-pyridazin-3-ylidene) -hydrazone; N-formyl (2- (2-amino-ethyl) -2H-pyridazin-3-ylidene) -hydrazone; N-formyl (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-formyl (6-pyrrolidino-2-methyl-2H-pyridazin-3-ylidene) - hydrazone; N-formyl (6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-formyl (5-amino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone
• Acide N-methanesulfonique (2-Methyl~2H-pyridazin-3-ylidene)-hydrazone ; Acide N-methanesulfonique (2-hydroxyethyl-2H-pyridazin-3-ylidene)-hydrazone ; Acide N-methanesulfonique (2-(2-amino-ethyl)-2H-pyridazin-3-ylidene)-hydrazone ; Acide N- methanesulfonique (6-méthoxy-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone ; Acide N- methanesulfonique (6-pyrrolidino-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone ; Acide N-methanesulfonique (6-phényl-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone ; Acide N-methanesulfonique (5-amino-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone.• N-methanesulfonic acid (2-Methyl ~ 2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (2-hydroxyethyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (2- (2-amino-ethyl) -2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (6-pyrrolidino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-methanesulfonic acid (5-amino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone.
• Acide N-phenyIsulfonique (2-Methyl-2H-pyridazin-3-ylidene)-hydrazone ; Acide N- N-phenyIsulfonique (2-hydroxyethyl-2H-pyridazin-3-ylidene)-hydrazone ; Acide N-phenyIsulfonique (2-(2-amino-ethyl)-2H-pyridazin-3-ylidene)-hydrazone ; Acide N-phenyIsulfonique (6-méthoxy-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone ; Acide N- phenylsulfonique (6-pyrrolidino-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone ; ; Acide N-phenyIsulfonique (6-phényl-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone ; ; Acide N- phenylsulfonique (5-amino-2-méthyl-2H-pyridazin-3-ylidene)-hydrazone. A titre d'exemple de composés de formule (Ib), appelés les (N- R1-2H- pyrazin-3-ylidene)-hydrazones, on peut citer: • N-Methyl-2H-pyrazin-2-ylidene-hydrazone ; N-hydroxyethyl-2H-pyrazin-2- ylidene-hydrazone ; N-(2-amino-ethyl)-2H-pyrazin-2-ylidene-hydrazone ; 3-méthoxy-N- méthyl-2H- pyrazin-2-ylidene-hydrazone ; 3-pyrrolidino-N-méthyl-2H-pyrazin-2-ylidene- hydrazone ; 3-phényl-N-méthyl-2H-pyrazin-2-ylidene-hydrazone . • N-acetyl (N-Methyl-2H-pyrazin-2-ylidene)-hydrazone ; N-acetyl (N- hydroxyethyl-2H- pyrazin-2-ylidene)-hydrazone ; N-acetyl (N-(2-amino-ethyl)-2H- pyrazin-2-ylidene)-hydrazone ; N-acetyl (3-méthoxy-N-méthyl-2H- pyrazin-2-ylidene)- hydrazone ; N-acetyl (3-pyrrolidino-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; N- acetyl (3-phényl-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; N-acetyl (3-amino-N- méthyl-2H-pyrazin-2-ylidene)-hydrazone• N-phenyIsulfonic acid (2-Methyl-2H-pyridazin-3-ylidene) -hydrazone; N-N-phenylsulfonic acid (2-hydroxyethyl-2H-pyridazin-3-ylidene) -hydrazone; N-phenysulfonic acid (2- (2-amino-ethyl) -2H-pyridazin-3-ylidene) -hydrazone; N-phenylsulfonic acid (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; N-phenylsulfonic acid (6-pyrrolidino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; ; N-phenylsulfonic acid (6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone; ; N-phenylsulfonic acid (5-amino-2-methyl-2H-pyridazin-3-ylidene) -hydrazone. By way of example of compounds of formula (Ib), called the (N- R1-2H- pyrazin-3-ylidene) -hydrazones, there may be mentioned: • N-Methyl-2H-pyrazin-2-ylidene-hydrazone; N-hydroxyethyl-2H-pyrazin-2-ylidene-hydrazone; N- (2-amino-ethyl) -2H-pyrazin-2-ylidene-hydrazone; 3-methoxy-N-methyl-2H-pyrazin-2-ylidene-hydrazone; 3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene-hydrazone; 3-phenyl-N-methyl-2H-pyrazin-2-ylidene-hydrazone. • N-acetyl (N-Methyl-2H-pyrazin-2-ylidene) -hydrazone; N-acetyl (N-hydroxyethyl-2H-pyrazin-2-ylidene) -hydrazone; N-acetyl (N- (2-amino-ethyl) -2H-pyrazin-2-ylidene) -hydrazone; N-acetyl (3-methoxy-N-methyl-2H-pyrazin-2-ylidene) - hydrazone; N-acetyl (3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-acetyl (3-phenyl-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-acetyl (3-amino-N- methyl-2H-pyrazin-2-ylidene) -hydrazone
• N-formyl (N-Methyl-2H-pyrazin-2-ylidene)-hydrazone ; N-formyl (N- hydroxyethyl-2H- pyrazin-2-ylidene)-hydrazone ; N-formyl (N-(2-amino-ethyl)-2H- pyrazin-2-ylidene)-hydrazone ; N-formyl (3-méthoxy-N-méthyl-2H- pyrazin-2-ylidene)- hydrazone ; N-formyl (3-pyrrolidino-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; N- formyl (3-phényl-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; N-formyl (3-amino-N- méthyl-2H-pyrazin-2-ylidene)-hydrazone• N-formyl (N-Methyl-2H-pyrazin-2-ylidene) -hydrazone; N-formyl (N-hydroxyethyl-2H-pyrazin-2-ylidene) -hydrazone; N-formyl (N- (2-amino-ethyl) -2H-pyrazin-2-ylidene) -hydrazone; N-formyl (3-methoxy-N-methyl-2H-pyrazin-2-ylidene) - hydrazone; N-formyl (3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-formyl (3-phenyl-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-formyl (3-amino-N- methyl-2H-pyrazin-2-ylidene) -hydrazone
• Acide N-methanesulfonique (N-Methyl-2H-pyrazin-2-ylidene)-hydrazone ; Acide N-methanesulfonique (N-hydroxyethyl-2H- pyrazin-2-ylidene)-hydrazone ; Acide N-methanesulfonique (N-(2-amino-ethyl)-2H-pyrazin-2-ylidene)-hydrazone ; Acide N- methanesulfonique (3-méthoxy-N-méthyl-2H- pyrazin-2-ylidene)-hydrazone ; Acide N- methanesulfonique (3-pyrrolidino-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; Acide N- methanesulfonique (3-phényl-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; Acide N- methanesulfonique (3-amino-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone.• N-methanesulfonic acid (N-Methyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (N-hydroxyethyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (N- (2-amino-ethyl) -2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-methoxy-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-phenyl-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-methanesulfonic acid (3-amino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone.
• Acide N-phenyIsulfonique (N-Methyl-2H-pyrazin-2-ylidene)-hydrazone ; Acide N-phenyIsulfonique (N-hydroxyethyl-2H- pyrazin-2-ylidene)-hydrazone ; Acide N- phenylsulfonique (N-(2-amino-ethyl)-2H-pyrazin-2-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-méthoxy-N-méthyl-2H- pyrazin-2-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-pyrrolidino-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-phényl-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-amino-N-méthyl-2H-pyrazin-2-ylidene)-hydrazone.• N-phenyIsulfonic acid (N-Methyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (N-hydroxyethyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (N- (2-amino-ethyl) -2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-methoxy-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-pyrrolidino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-phenyl-N-methyl-2H-pyrazin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-amino-N-methyl-2H-pyrazin-2-ylidene) -hydrazone.
A titre d'exemple de composés de formule (le), appelés les (N-R1-2H- pyrimidin-3-ylidene)-hydrazohes, on peut citer : • N-Methyl-2H-pyrimidin-2-ylidene-hydrazone ; N-hydroxyethyl-2H-pyrimidin-2- ylidene-hydrazone ; N-(2-amino-ethyl)-2H-pyrimidin-2-ylidene-hydrazone ; 4-méthoxy- N-méthyl-2H- pyrimidin-2-ylidene-hydrazone ; 4,6-diméthoxy-N-méthyl-2H- pyrimidin-2- ylidene-hydrazone ; 4-pyrrolidino-N-méthyl-2H-pyrimidin-2-ylidene-hydrazone ; 4- phényl-N-méthyl-2H-pyrimidin-2-ylidene-hydrazone ; 4-amino-N-méthyl-2H-pyrimidin-2- ylidene-hydrazone.By way of example of compounds of formula (Ic), called the (N-R1-2H- pyrimidin-3-ylidene) -hydrazohes, there may be mentioned: • N-Methyl-2H-pyrimidin-2-ylidene-hydrazone; N-hydroxyethyl-2H-pyrimidin-2-ylidene-hydrazone; N- (2-amino-ethyl) -2H-pyrimidin-2-ylidene-hydrazone; 4-methoxy-N-methyl-2H-pyrimidin-2-ylidene-hydrazone; 4,6-dimethoxy-N-methyl-2H-pyrimidin-2-ylidene-hydrazone; 4-pyrrolidino-N-methyl-2H-pyrimidin-2-ylidene-hydrazone; 4-phenyl-N-methyl-2H-pyrimidin-2-ylidene-hydrazone; 4-amino-N-methyl-2H-pyrimidin-2-ylidene-hydrazone.
• N-acetyl (N-Methyl-2H-pyrimidin-2-ylidene)-hydrazone ; N-acetyl (N- hydroxyethyl-2H- pyrimidin-2-ylidene)-hydrazone ; N-acetyl (N-(2-amino-ethyl)-2H- pyrimidin-2-ylidene)-hydrazone ; N-acetyl (4-méthoxy-N-méthyl-2H- pyrimidin-2- ylidene)-hydrazone ; N-acetyl (4,6-diméthoxy-N-méthyl-2H- pyrimidin-2-ylidene)- hydrazone ; N-acetyl (4-pyrrolidino-N-méthyl-2H-pyrimidin-2-ylidene)-hydrazone ; N- acetyl (4-phényl-N-méthyl-2H-pyrimidin-2-ylidene)-hydrazone ; N-acetyl (4-amino-N- méthyl-2H-pyrimidin-2-ylidene)-hydrazone• N-acetyl (N-Methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-acetyl (N-hydroxyethyl-2H-pyrimidin-2-ylidene) -hydrazone; N-acetyl (N- (2-amino-ethyl) -2H-pyrimidin-2-ylidene) -hydrazone; N-acetyl (4-methoxy-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-acetyl (4,6-dimethoxy-N-methyl-2H-pyrimidin-2-ylidene) - hydrazone; N-acetyl (4-pyrrolidino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-acetyl (4-phenyl-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-acetyl (4-amino-N- methyl-2H-pyrimidin-2-ylidene) -hydrazone
• N-formyl (N-Methyl-2H-pyrimidin-2-ylidene)-hydrazone ; N-formyl (N- hydroxyethyl-2H- pyrimidin-2-ylidene)-hydrazone ; N-formyl (N-(2-amino-ethyl)-2H- pyrimidin-2-ylidene)-hydrazone ; N-formyl (4-méthoxy-N-méthyl-2H- pyrimidin-2- ylidene)-hydrazone ; ; N-formyl (4,6-diméthoxy-N-méthyl-2H- pyrimidin-2-ylidene)- hydrazone ; N-formyl (4-pyrrolidino-N-méthyl-2H-pyrimidin-2-ylidene)-hydrazone ; N- formyl (4-phényl-N-méthyl-2H-pyrimidin-2-ylidene)-hydrazone ; N-formyl (4-amino-N- méthyl-2H-pyrimidin-2-ylidene)-hydrazone• N-formyl (N-Methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-formyl (N-hydroxyethyl-2H-pyrimidin-2-ylidene) -hydrazone; N-formyl (N- (2-amino-ethyl) -2H-pyrimidin-2-ylidene) -hydrazone; N-formyl (4-methoxy-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; ; N-formyl (4,6-dimethoxy-N-methyl-2H-pyrimidin-2-ylidene) - hydrazone; N-formyl (4-pyrrolidino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-formyl (4-phenyl-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-formyl (4-amino-N- methyl-2H-pyrimidin-2-ylidene) -hydrazone
• Acide N-methanesulfonique (N-Methyl-2H-pyrimidin-2-ylidene)-hydrazone ; Acide N-methanesulfonique (N-hydroxyethyl-2H- pyrimidin-2-ylidene)-hydrazone ; Acide N-methanesulfonique (N-(2-amino-ethyl)-2H-pyrimidin-2-ylidene)-hydrazone ; Acide N-methanesulfonique (4-méthoxy-N-méthyl-2H- pyrimidin-2-ylidene)- hydrazone ; ; Acide N-methanesulfonique (4,6-diméthoxy-N-méthyl-2H- pyrimidin-2- ylidene)-hydrazone ; Acide N-methanesulfonique (4-pyrrolidino-N-méthyl-2H-pyrimidin- 2-ylidene)-hydrazone ; Acide N-methanesulfonique (4-phényl-N-méthyl-2H-pyrimidin- 2-ylidene)-hydrazone ; Acide N-methanesulfonique (4-amino-N-méthyl-2H-pyrimidin-2- ylidene)-hydrazone. • Acide N-phenyIsulfonique (N-Methyl-2H-pyrimidin-2-ylidene)-hydrazone ;• N-methanesulfonic acid (N-Methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (N-hydroxyethyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (N- (2-amino-ethyl) -2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (4-methoxy-N-methyl-2H-pyrimidin-2-ylidene) - hydrazone; ; N-methanesulfonic acid (4,6-dimethoxy-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (4-pyrrolidino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (4-phenyl-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-methanesulfonic acid (4-amino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone. • N-phenyIsulfonic acid (N-Methyl-2H-pyrimidin-2-ylidene) -hydrazone;
Acide N- N-phenyIsulfonique (N-hydroxyethyl-2H- pyrimidin-2-ylidene)-hydrazone ; Acide N-phenyIsulfonique (N-(2-amino-ethyl)-2H-pyrimidin-2-ylidene)-hydrazone ; Acide N-phenyIsulfonique (3-méthoxy-N-méthyl-2H- pyrimidin-2-ylidene)-hydrazone ; Acide N-phenyIsulfonique (3-pyrrolidino-N-méthyl-2H-pyrimidin-2-ylidene)-hydrazone ; Acide N-phenyIsulfonique (3-phényl-N-méthyl-2H-pyrimidin-2-ylidene)-hydrazone ; Acide N-phenyIsulfonique (3-amino-N-méthyl-2H-pyrimidin-2-ylidene)-hydrazone. Pour la formule (Id), on peut citer nommément, les (3-R1-2H-pyrimidin-4- ylidene)-hydrazonesN-N-phenylsulfonic acid (N-hydroxyethyl-2H-pyrimidin-2-ylidene) -hydrazone; N-phenylsulfonic acid (N- (2-amino-ethyl) -2H-pyrimidin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-methoxy-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-pheny-sulfonic acid (3-pyrrolidino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-phenylsulfonic acid (3-phenyl-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone; N-phenysulfonic acid (3-amino-N-methyl-2H-pyrimidin-2-ylidene) -hydrazone. For the formula (Id), there may be mentioned by name, the (3-R1-2H-pyrimidin-4-ylidene) -hydrazones
• 3-Methyl-2H-pyrimidin-4-ylidene-hydrazone ; 3-hydroxyethyl-2H-pyrimidin-4- ylidene-hydrazone ; 3-(2-amino-ethyl)-2H-pyrimidin-4-ylidene-hydrazone ; 3-méthyl-5- méthoxy-2H- pyrimidin-4-ylidene-hydrazone ; 3-méthyl-5-pyrrolidino-2H-pyrimidin-4- ylidene-hydrazone ; 3-méthyl-5-phényl-2H-pyrimidin-4-ylidene-hydrazone ; 3-méthyl-5- amino-2H-pyrimidin-4-ylidene-hydrazone.• 3-Methyl-2H-pyrimidin-4-ylidene-hydrazone; 3-hydroxyethyl-2H-pyrimidin-4-ylidene-hydrazone; 3- (2-amino-ethyl) -2H-pyrimidin-4-ylidene-hydrazone; 3-methyl-5-methoxy-2H-pyrimidin-4-ylidene-hydrazone; 3-methyl-5-pyrrolidino-2H-pyrimidin-4-ylidene-hydrazone; 3-methyl-5-phenyl-2H-pyrimidin-4-ylidene-hydrazone; 3-methyl-5-amino-2H-pyrimidin-4-ylidene-hydrazone.
• N-acetyl (3-Methyl-2H-pyrimidin-4-ylidene)-hydrazone ; N-acetyl (3- hydroxyethyl-2H-pyrimidin-4-ylidene)-hydrazone ; N-acetyl (3-(2-amino-ethyl)-2H- pyrimidin-4-ylidene)-hydrazone ; N-acetyl (3-méthyl-5-méthoxy-2H- pyrimidin-4- ylidene)-hydrazone ; N-acetyl (3-méthyl-5-pyrrolidino-2H-pyrimidin-4-ylidene)- hydrazone ; N-acetyl (3-méthyl-5-phényl-2H-pyrimidin-4-ylidene)-hydrazone ; N-acetyl (3-méthyl-5-amino-2H-pyrimidin-4-ylidene)-hydrazone.• N-acetyl (3-Methyl-2H-pyrimidin-4-ylidene) -hydrazone; N-acetyl (3-hydroxyethyl-2H-pyrimidin-4-ylidene) -hydrazone; N-acetyl (3- (2-amino-ethyl) -2H-pyrimidin-4-ylidene) -hydrazone; N-acetyl (3-methyl-5-methoxy-2H-pyrimidin-4-ylidene) -hydrazone; N-acetyl (3-methyl-5-pyrrolidino-2H-pyrimidin-4-ylidene) - hydrazone; N-acetyl (3-methyl-5-phenyl-2H-pyrimidin-4-ylidene) -hydrazone; N-acetyl (3-methyl-5-amino-2H-pyrimidin-4-ylidene) -hydrazone.
• N-formyl (3-Methyl-2H-pyrimidin-4-ylidene)-hydrazone ; N-formyl (3- hydroxyethyl-2H-pyrimidin-4-ylidene)-hydrazone ; N-formyl (3-(2-amino-ethyl)-2H- pyrimidin-4-ylidene)-hydrazone ; N-formyl (3-méthyl-5-méthoxy-2H- pyrimidin-4- ylidene)-hydrazone ; N-formyl (3-méthyl-5-pyrrolidino-2H-pyrimidin-4-ylidene)- hydrazone ; N-formyl (3-méthyl-5-phényl-2H-pyrimidin-4-ylidene)-hydrazone ; N-formyl (3-méthyl-5-amino-2H-pyrimidin-4-ylidene)-hydrazone.• N-formyl (3-Methyl-2H-pyrimidin-4-ylidene) -hydrazone; N-formyl (3-hydroxyethyl-2H-pyrimidin-4-ylidene) -hydrazone; N-formyl (3- (2-amino-ethyl) -2H-pyrimidin-4-ylidene) -hydrazone; N-formyl (3-methyl-5-methoxy-2H-pyrimidin-4-ylidene) -hydrazone; N-formyl (3-methyl-5-pyrrolidino-2H-pyrimidin-4-ylidene) - hydrazone; N-formyl (3-methyl-5-phenyl-2H-pyrimidin-4-ylidene) -hydrazone; N-formyl (3-methyl-5-amino-2H-pyrimidin-4-ylidene) -hydrazone.
• Acide N-methanesulfonique (3-Methyl-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N-methanesulfonique (3-hydroxyethyl-2H-pyrimidin-4-ylidene)-hydrazone ; Acide• N-methanesulfonic acid (3-Methyl-2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-hydroxyethyl-2H-pyrimidin-4-ylidene) -hydrazone; Acid
N-methanesulfonique (3-(2-amino-ethyl)-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N- methanesulfonique (3-méthyl-5-méthoxy-2H- pyrimidin-4-ylidene)-hydrazone ; Acide N- methanesulfonique (3-méthyl-5-pyrrolidino-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N-methanesulfonique (3-méthyl-5-phényl-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N- methanesulfonique (3-méthyl-5-amino-2H-pyrimidin-4-ylidene)-hydrazone.N-methanesulfonic (3- (2-amino-ethyl) -2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-methoxy-2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-pyrrolidino-2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-phenyl-2H-pyrimidin-4-ylidene) -hydrazone; N-methanesulfonic acid (3-methyl-5-amino-2H-pyrimidin-4-ylidene) -hydrazone.
• Acide N-phenyIsulfonique (3-Methyl-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-hydroxyethyl-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-(2-amino-ethyl)-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-méthyl-5-méthoxy-2H- pyrimidin-4-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-méthyl-5-pyrrolidino-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-méthyl-5-phényl-2H-pyrimidin-4-ylidene)-hydrazone ; Acide N- phenylsulfonique (3-méthyl-5-amino-2H-pyrimidin-4-ylidene)-hydrazone.• N-phenyIsulfonic acid (3-Methyl-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-hydroxyethyl-2H-pyrimidin-4-ylidene) -hydrazone; N- acid phenylsulfonic (3- (2-amino-ethyl) -2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-methoxy-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-pyrrolidino-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-phenyl-2H-pyrimidin-4-ylidene) -hydrazone; N-phenylsulfonic acid (3-methyl-5-amino-2H-pyrimidin-4-ylidene) -hydrazone.
Selon un mode de réalisation particulier, la base d'oxydation de type hydrazone correspond à la formule suivante :According to a particular embodiment, the hydrazone type oxidation base corresponds to the following formula:
Figure imgf000012_0001
laquelle R1 est un radical alkyle, A, R2 et R4 sont l'hydrogène, et R5 est un radical alcoxy, phényle ou pyrrolidine. Dans ce cas particulier, le composé hydrazone est choisi parmi 6-méthoxy-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone, 6-(pyrrolidin-N- yl)-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone, 6-phényl-2-méthyl-2H- pyridazin-3- ylidene)-hydrazone.
Figure imgf000012_0001
which R1 is an alkyl radical, A, R2 and R4 are hydrogen, and R5 is an alkoxy, phenyl or pyrrolidine radical. In this particular case, the hydrazone compound is chosen from 6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone, 6- (pyrrolidin-N- yl) -2-methyl-2H-pyridazin-3- ylidene) -hydrazone, 6-phenyl-2-methyl-2H-pyridazin-3-ylidene) -hydrazone.
Les composés de formules (I) utiles dans la composition de la présente invention peuvent être obtenus à partir des procédés de préparation décrits par exemple dans la publication HUNIG S., MULLER F. ; Liebigs Ann. Chem., BD651,The compounds of formulas (I) useful in the composition of the present invention can be obtained from the preparation methods described for example in the publication HUNIG S., MULLER F.; Liebigs Ann. Chem., BD651,
1962, 97-98a.1962, 97-98a.
Le coupleur utile dans la composition de la présente invention est un coupleur conventionnellement utilisé pour la teinture de fibres kératiniques. Parmi ces coupleurs, on peut notamment citer les métaphénylènediamines, les méta- aminophénols, les métadiphénols et les coupleurs hétérocycliques.The coupler useful in the composition of the present invention is a coupler conventionally used for dyeing keratin fibers. Among these couplers, mention may in particular be made of metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers.
Parmi les coupleurs hétérocycliques utilisables dans la composition tinctoriale conforme à l'invention, on peut notamment citer les dérivés indoliques, les dérivés indoliniques, les dérivés de benzimidazole, les dérivés de benzomorpholine, les dérivés de sésamol, les dérivés pyrazolo-azoliques, les dérivés pyrrolo-azoliques, les dérivés imidazolo-azoliques, les dérivés pyrazolo-pyrimidiniques, les dérivés de pyrazolin-3,5-diones, les dérivés pyrrolo-[3,2-d]-oxazoliques, les dérivés pyrazolo-[3,4- d]-thiazoliques, les dérivés S-oxyde-thiazolo-azoliques, les dérivés S,S-dioxyde- thiazolo-azoliques, et leurs sels d'addition avec un acide. A titre d'exemple, on peut citer le 2-méthyl 5-aminophénol, le 5-N-(β- hydroxyéthyl)amino 2-méthyl phénol, le 6-chloro-2-méthyl-5-aminophénol, le 3-amino phénol, le 1 ,3-di hydroxy benzène, le 1 ,3-dihydroxy 2-méthyl benzène, le 4-chloro 1 ,3- dihydroxy benzène, le 2,4-diamino l-(β-hydroxyéthyloxy) benzène, le 2-amino 4-(β- hydroxyéthylamino) 1 -méthoxybenzène, le 1 ,3-diamino benzène, le 1 ,3-bis-(2,4- diaminophénoxy) propane, la 3-uréido aniline, le 3-uréido 1-diméthylamino benzène, le sésamol, le 1-β-hydroxyéthylamino-3,4-méthylènedioxybenzène, l' -naphtol, le 2 méthyl-1-naphtol, le 6-hydroxy indole, le 4-hydroxy indole, le 4-hydroxy N-méthyl indole, la 2-amino-3-hydroxy pyridine, la 6- hydroxy benzomorpholine la 3,5-diamino- 2,6-diméthoxypyridine, le 1-N-(β-hydroxyéthyl)amino-3,4-méthylène dioxybenzène, le 2,6-bis-(β-hydroxyéthylamino)toluène et leurs sels d'addition.Among the heterocyclic couplers which can be used in the dye composition in accordance with the invention, mention may in particular be made of indole derivatives, indoline derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyrazolo-azole derivatives, derivatives pyrroloazoles, imidazolo-azole derivatives, pyrazolo-pyrimidine derivatives, pyrazolin-3,5-diones derivatives, pyrrolo- [3,2-d] -oxazole derivatives, pyrazolo- [3,4- derivatives d] -thiazolics, the S-oxide-thiazolo-azolic derivatives, the S, S-dioxide-thiazolo-azolic derivatives, and their addition salts with an acid. By way of example, mention may be made of 2-methyl 5-aminophenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 1, 3-di hydroxy benzene, 1, 3-dihydroxy 2-methyl benzene, 4-chloro 1, 3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2 -amino 4- (β- hydroxyethylamino) 1 -methoxybenzene, 1, 3-diamino benzene, 1, 3-bis- (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, -naphthol, 2 methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts.
Dans la composition de la présente invention, le ou les composés de formule (I) sont chacun présents de préférence en quantité comprise entre 0,001 et 10 %, plus prèférentiellement entre 0,005 et 6 % en poids du poids total de la composition tinctoriale et le ou les coupleurs sont présents en quantité de préférence comprise entre 0,001 et 10 %, plus prèférentiellement de 0,005 à 6 % en poids du poids total de la composition tinctoriale.In the composition of the present invention, the compound or compounds of formula (I) are each preferably present in an amount of between 0.001 and 10%, more preferably between 0.005 and 6% by weight of the total weight of the dye composition and the or the couplers are present in an amount preferably of between 0.001 and 10%, more preferably from 0.005 to 6% by weight of the total weight of the dye composition.
La composition selon la présente invention peut de plus comprendre une ou plusieurs bases d'oxydation additionnelles différentes des bases d'oxydation de formule (I). Ces bases d'oxydation additionnelles sont choisies parmi les bases d'oxydation classiquement utilisées en teinture d'oxydation, par exemple les paraphénylènediamines, les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols et les bases hétérocycliques.The composition according to the present invention may also comprise one or more additional oxidation bases different from the oxidation bases of formula (I). These additional oxidation bases are chosen from the oxidation bases conventionally used in oxidation dyeing, for example paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Parmi les paraphénylènediamines, on peut citer à titre d'exemple, la paraphénylènediamine, la paratoluylènediamine, la 2-chloro paraphénylènediamine, la 2,3-diméthyl paraphénylènediamine, la 2,6-diméthyl paraphénylènediamine, la 2,6- diéthyl paraphénylènediamine, la 2,5-diméthyl paraphénylènediamine, la N,N-diméthyl paraphénylènediamine, la N,N-diéthyl paraphénylènediamine, la N,N-dipropyl paraphénylènediamine, la 4-amino N,N-diéthyl 3-méthyl aniline, la N,N-bis-(β- hydroxyéthyl) paraphénylènediamine, la 4-N,N-bis-(β-hydroxyéthyl)amino 2-méthyl aniline, la 4-N,N-bis-(β-hydroxyéthyl)amino 2-chloro aniline, la 2-β-hydroxyéthyl paraphénylènediamine, la 2-fluoro paraphénylènediamine, la 2-isopropyl paraphénylènediamine, la N-(β-hydroxypropyl) paraphénylènediamine, laAmong the paraphenylenediamines, there may be mentioned by way of example, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N- bis- (β- hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline, 2-β-hydroxyethyl paraphenylenediamine, 2-fluoro paraphenylenediamine, 2-isopropyl paraphenylenediamine, N- (β-hydroxypropyl) paraphenylenediamine,
2-hydroxyméthyl paraphénylènediamine, la N,N-diméthyl 3-méthyl paraphénylènediamine, la N,N-(éthyl, β-hydroxyéthyl) paraphénylènediamine, la N-(β,γ- dihydroxypropyl) paraphénylènediamine, la N-(4'-aminophényl) paraphénylènediamine, la N-phényl paraphénylènediamine, la 2-β-hydroxyéthyloxy paraphénylènediamine, la 2-β-acétylaminoéthyloxy paraphénylènediamine, la N-(β-méthoxyéthyl) paraphénylènediamine, et leurs sels d'addition avec un acide.2-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl para-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) para-phenylenediamine, N- (β, γ-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, and their addition salts with an acid.
Parmi les paraphénylènediamines citées ci-dessus, la paraphénylènediamine, la paratoluylènediamine, la 2-isopropyl paraphénylènediamine, la 2-β-hydroxyéthyl paraphénylènediamine, la 2-β-hydroxyéthyloxy paraphénylènediamine, la 2,6-diméthyl paraphénylènediamine, la 2,6-diéthyl paraphénylènediamine, la 2,3-diméthyl paraphénylènediamine, la N,N-bis-(β- hydroxyéthyl) paraphénylènediamine, la 2-chloro paraphénylènediamine, la 2-β-acétylaminoéthyloxy paraphénylènediamine, et leurs sels d'addition avec un acide sont particulièrement préférées.Among the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred .
Parmi les bis-phénylalkylènediamines, on peut citer à titre d'exemple, le N,N'-bis-(β-hydroxyéthyl) N,N'-bis-(4'-aminophényl) 1,3-diamino propanol, la N,N'-bis- (β-hydroxyéthyl) N,N'-bis-(4'-aminophényl) éthylènediamine, la N,N'-bis-(4- aminophényl) tétraméthylènediamine, la N,N'-bis-(β-hydroxyéthyl) N,N'-bis-(4- aminophényl) tétraméthylènediamine, la N,N'-bis-(4-méthyl-aminophényl) tétraméthylènediamine, la N,N'-bis-(éthyl) N,N'-bis-(4'-amino, 3'-méthylphényl) éthylènediamine, le 1 ,8-bis-(2,5-diamino phénoxy)-3,6-dioxaoctane, et leurs sels d'addition avec un acide.Among the bis-phenylalkylenediamines, there may be mentioned by way of example, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N , N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methyl-aminophenyl) 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.
Parmi les para-aminophénols, on peut citer à titre d'exemple, le para- aminophénol, le 4-amino 3-méthyl phénol, le 4-amino 3-fluoro phénol, le 4-amino 3- hydroxyméthyl phénol, le 4-amino 2-méthyl phénol, le 4-amino 2-hydroxyméthyl phénol, le 4-amino 2-méthoxyméthyl phénol, le 4-amino 2-aminométhyl phénol, le 4-amino 2-(β- hydroxyéthyl aminométhyl) phénol, le 4-amino 2-fluoro phénol, et leurs sels d'addition avec un acide.Among the para-aminophenols, there may be mentioned by way of example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid.
Parmi les ortho-aminophénols, on peut citer à titre d'exemple, le 2-amino phénol, le 2-amino 5-méthyl phénol, le 2-amino 6-méthyl phénol, le 5-acétamido 2-amino phénol, et leurs sels d'addition avec un acide.Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.
Parmi les bases hétérocycliques, on peut citer à titre d'exemple, les dérivés pyridiniques, les dérivés pyrimidiniques et les dérivés pyrazoliques.Among the heterocyclic bases that may be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Parmi les dérivés pyridiniques, on peut citer les composés décrits par exemple dans les brevets GB 1 026 978 et GB 1 153 196, comme la 2,5-diamino pyridine, la 2-(4-méthoxyphényl)amino 3-amino pyridine, la 2,3-diamino 6-méthoxy pyridine, la 2-(β-méthoxyéthyl)amino 3-amino 6-méthoxy pyridine, la 3,4-diamino pyridine, et leurs sels d'addition avec un acide.Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.
Parmi les dérivés pyrimidiniques, on peut citer les composés décrits par exemple dans les brevets DE 2 359 399 ; JP 88-169 571 ; JP 05 163 124 ; EP 0 770 375 ou demande de brevet WO 96/15765 comme la 2,4,5,6-tétra-aminopyrimidine, la 4-hydroxy 2,5,6-triaminopyrimidine, la 2-hydroxy 4,5,6-triaminopyrimidine, la 2,4-dihydroxy 5,6-diaminopyrimidine, la 2,5,6-triaminopyrimidine, et les dérivés pyrazolo-pyrimidiniques tels ceux mentionnés dans la demande dé brevet FR-A-2 750 048 et parmi lesquels on peut citer la pyrazolo-[1,5-a]-pyrimidine-3,7-diamine ; la 2,5- diméthyl pyrazolo-[1 ,5-a]-pyrimidine-3,7-diamine ; la pyrazolo-[1 ,5-a]-pyrimidine-3,5- diamine ; la 2,7-diméthyl pyrazolo-[1 ,5-a]-pyrimidine-3,5-diamine ; le 3-amino pyrazolo- [1 ,5-a]-pyrimidin-7-ol ; le 3-amino pyrazo,lo-[1 ,5-a]-pyrimidin-5-ol ; le 2-(3-amino pyrazolo-[1 ,5-a]-pyrimidin-7-ylamino)-éthanol, le 2-(7-amino pyrazolo-[1 ,5-a]-pyrimidin- 3-ylamino)-éthanol, le 2-[(3-amino-pyrazolo[1 ,5-a]pyrimidin-7-yl)-(2-hydroxy-éthyl)- aminoj-éthanol, le 2-[(7-amino-pyrazolo[1 ,5-a]pyrimidin-3-yl)-(2-hydroxy-éthyl)-amino]- éthanol, la 5,6-diméthyl pyrazolo-[1,5-a]-pyrimidine-3,7-diamine, la 2,6-diméthyl pyrazolo-[1 ,5-a]-pyrimidine-3,7-diamine, la 2, 5, N 7, N 7-tetraméthyl pyrazolo-[1 ,5-a]- pyrimidine-3,7-diamine, la 3-amino-5-méthyl-7-imidazolylpropylamino pyrazolo-[1 ,5-a]- pyrimidine et leurs sels d'addition avec un acide et leurs formes tautomères, lorsqu'il existe un équilibre tautomérique.Among the pyrimidine derivatives, mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned 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 pyrazo, lo- [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-hydroxy-ethyl) - aminoj-ethanol, 2 - [(7-amino-pyrazolo [1 , 5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] - ethanol, 5,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, la 2, 5, N 7, N 7-tetramethyl pyrazolo- [1,5-a] - pyrimidine-3,7 -diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1, 5-a] - pyrimidine and their addition salts with an acid and their tautomeric forms, when there is a tautomeric equilibrium.
Parmi les dérivés pyrazoliques, on peut citer les composés décrits dans les brevets DE 3 843 892, DE 4 133 957 et demandes de brevet WO 94/08969, WO 94/08970, FR-A-2 733 749 et DE 195 43 988 comme le 4,5-diamino 1-méthyl pyrazole, le 4,5-diamino l-(β-hydroxyéthyl) pyrazole, le 3,4-diamino pyrazole, le 4,5- diamino 1-(4'-chlorobenzyl) pyrazole, le 4,5-diamino 1 ,3-diméthyl pyrazole, le 4,5-diamino 3-méthyl 1 -phényl pyrazole, le 4,5-diamino 1-méthyl 3-phényl pyrazole, le 4-amino 1,3-diméthyl 5-hydrazino pyrazole, le 1-benzyl 4,5-diamino 3-méthyl pyrazole, le 4,5-diamino 3-tert-butyl 1-méthyl pyrazole, le 4,5-diamino 1-tert-butyl 3-méthyl pyrazole, le 4,5-diamino l-(β-hydroxyéthyl) 3-méthyl pyrazole, le 4,5-diamino 1-éthyl 3- méthyl pyrazole, le 4,5-diamino 1-éthyl 3-(4'-méthoxyphényl) pyrazole, le 4,5-diamino 1- éthyl 3-hydroxyméthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-méthyl pyrazole, le 4,5-diamino 3-hydroxyméthyl 1-isopropyl pyrazole, le 4,5-diamino 3-méthyl 1-isopropyl pyrazole, le 4-amino 5-(2'-aminoéthyl)amino 1,3-diméthyl pyrazole, le 3,4,5-triamino pyrazole, le 1-méthyl 3,4,5-triamino pyrazole, le 3,5-diamino 1-méthyl 4-méthylamino pyrazole, le 3,5-diamino 4-(β-hydroxyéthyl)amino 1-méthyl pyrazole, et leurs sels d'addition avec un acide.Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- (β-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-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole , 4,5-diamino l- (β-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-diamin o 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- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid.
Dans la composition de la présente invention, la base additionnelle est présente en quantité de préférence comprise entre 0,001 et 10 % en poids environ du poids total de la composition tinctoriale et encore plus prèférentiellement de 0,005 à 6In the composition of the present invention, the additional base is present in an amount preferably between 0.001 and 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 6
%.%.
D'une manière générale, les sels d'addition avec un acide utilisables dans le cadre des compositions tinctoriales de l'invention pour les bases d'oxydation et les coupleurs sont notamment choisis parmi les chlorhydrates, les bromhydrates, les sulfates, les citrates, les succinates, les tartrates, les lactates, les tosylates, les benzènesulfonates, les phosphates et les acétates.In general, the addition salts with an acid which can be used in the context of the dye compositions of the invention for the oxidation bases and the couplers are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
Les sels d'addition utilisables dans le cadre de l'invention sont par exemple choisis parmi les sels d'addition avec la soude, la potasse, l'ammoniaque, les aminés ou les alcanolamines. La composition tinctoriale conforme à l'invention peut en outre contenir un ou plusieurs colorants directs pouvant notamment être choisis parmi les colorants nitrés de la série benzénique, les colorants directs cationiques, les colorants directs azoïques, les colorants directs méthiniques.The addition salts which can be used in the context of the invention are for example chosen from addition salts with sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines. The dye composition in accordance with the invention may also contain one or more direct dyes which can in particular be chosen from nitro dyes of the benzene series, cationic direct dyes, azo direct dyes, methinic direct dyes.
Le milieu approprié pour la teinture appelé aussi support de teinture est généralement constitué par de l'eau ou par un mélange d'eau et d'au moins un solvant organique pour solubiliser les composés qui ne seraient pas suffisamment solubles dans l'eau. A titre de solvant organique, on peut par exemple citer les alcanols inférieurs en CrC4, tels que l'éthanol et l'isopropanol ; les polyols et éthers de polyols comme le 2-butoxyéthanol, le propylèneglycol, le monométhyléther de propylèneglycol, le monoéthyléther et le monométhyléther du diéthylèneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, et leurs mélanges.The medium suitable for dyeing, also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C r C 4 alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
Les solvants peuvent être présents dans des proportions de préférence comprises entre 1 et 40 % en poids environ par rapport au poids total de la composition tinctoriale, et encore plus prèférentiellement entre 5 et 30 % en poids environ.The solvents may be 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.
La composition tinctoriale conforme à l'invention peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux, tels que des agents tensio-actifs anioniques, cationiques, non-ioniques, amphotères, zwittérioniques ou leurs mélanges, des polymères anioniques, cationiques, non-ioniques, amphotères, zwittérioniques ou leurs mélanges, des agents épaississants minéraux ou organiques, et en particulier les épaississants associatifs polymères anioniques, cationiques, non ioniques et amphotères, des agents antioxydants, des agents de pénétration, des agents séquestrants, des parfums, des tampons, des agents dispersants, des agents de conditionnement tels que par exemple des silicones volatiles ou non volatiles, modifiées ou non modifiées, des agents filmogènes, des céramides, des agents conservateurs, des agents opacifiants.The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, agents mineral or organic thickeners, and in particular associative anionic, cationic, nonionic and amphoteric polymeric thickeners, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
Ces adjuvants ci dessus sont en général présents en quantité comprise pour chacun d'eux entre 0,01 et 20 % en poids par rapport au poids de la composition.These above adjuvants are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.
Bien entendu, l'homme de l'art veillera à choisir ce ou ces éventuels composés complémentaires de manière telle que les propriétés avantageuses attachées intrinsèquement à la composition de teinture d'oxydation conforme à l'invention ne soient pas, ou substantiellement pas, altérées par la ou les adjonctions envisagées.Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged.
Le pH de la composition tinctoriale conforme à l'invention est généralement compris entre 3 et 12 environ, et de préférence entre 5 et 11 environ. Il peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques ou bien encore à l'aide de systèmes tampons classiques.The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.
Parmi les agents acidifiants, on peut citer, à titre d'exemple, les acides minéraux ou organiques comme l'acide chlorhydrique, l'acide orthophosphorique, l'acide sulfurique, les acides carboxyliques comme l'acide acétique, l'acide tartrique, l'acide citrique, l'acide lactique, les acides sulfoniques.Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
Parmi les agents alcalinisants on peut citer, à titre d'exemple, l'ammoniaque, les carbonates alcalins, les alcanolamines telles que les mono-, di- et triéthanolamines ainsi que leurs dérivés, les hydroxydes de sodium ou de potassium et les composés de formule (III) suivante :Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below:
Figure imgf000017_0001
dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en 0,-04 ; R6, R7l R8 et R9, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en 0,-04 ou hydroxyalkyle en 0,-04. La composition tinctoriale selon l'invention peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels, ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humains. L'invention a également pour objet un procédé de teinture des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux mettant en œuvre la composition tinctoriale telle que définie précédemment.
Figure imgf000017_0001
in which W is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical in O, -0 4 ; R 6 , R 7l R 8 and R 9 , identical or different, represent a hydrogen atom, an alkyl radical at 0, -0 4 or hydroxyalkyl at 0, -0 4 . The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair. The invention also relates to a process for dyeing keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above.
Selon ce procédé, on applique sur les fibres la composition selon la présente invention telle que définie précédemment, la couleur étant révélée à l'aide d'un agent oxydant. La couleur peut être révélée à pH acide, neutre ou alcalin et l'agent oxydant peut être ajouté à la composition de l'invention juste au moment de l'emploi ou il peut être mis en œuvre à partir d'une composition oxydante le contenant, appliquée simultanément ou séquentiellement à la composition de l'invention sur les fibres.According to this process, the composition according to the present invention as defined above is applied to the fibers, the color being revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it , applied simultaneously or sequentially to the composition of the invention on the fibers.
Selon un mode de réalisation particulier, la composition selon la présente invention est mélangée, de préférence au moment de l'emploi, à une composition contenant, dans un milieu approprié pour la teinture, au moins un agent oxydant, cet agent oxydant étant présent en une quantité suffisante pour développer une coloration.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 enough to develop color.
Le mélange obtenu est ensuite appliqué sur les fibres kératiniques. Après un temps de pose de 3 à 50 minutes environ, de préférence 5 à 30 minutes environ, les fibres kératiniques sont rincées, lavées au shampooing, rincées à nouveau puis séchées.The mixture obtained is then applied to the keratin fibers. After an exposure time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.
Les agents oxydants classiquement utilisés pour la teinture d'oxydation des fibres kératiniques sont par exemple le peroxyde d'hydrogène, le peroxyde d'urée, les bramâtes de métaux alcalins, les persels tels que les perborates et persulfates, les peracides et les systèmes d'oxydations enzymatiques. Les systèmes d'oxydations enzymatiques sont par exemple choisis parmi les peroxydases, le cas échéant en présence d'au moins un donneur pour ces peroxydases, les oxydoréductases à 2 électrons en présence d'au moins un donneur pour ces oxydoréductases, et les oxydoréductases à 4 électrons.The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are for example hydrogen peroxide, urea peroxide, alkali metal bramates, persalts such as perborates and persulfates, peracids and d systems. 'enzymatic oxidations. The enzymatic oxidation systems are for example chosen from peroxidases, where appropriate in the presence of at least one donor for these peroxidases, oxidoreductases with 2 electrons in the presence of at least one donor for these oxidoreductases, and oxidoreductases with 4 electrons.
A titre d'oxydoréductases à 2 électrons, on peut citer les pyranose oxydases, les glucose oxydases, les glycérol oxydases, les lactate oxydases, les pyruvate oxydases et les uricases. A titre d'oxydoréductases à 4 électrons, on peut citer les laccases, les tyrosinases, les catéchol oxydases et les polyphénol oxydases. A titre de peroxydases, on peut citer les NADH peroxydases, les acides gras peroxydases, les NADPH peroxydases, les cytochrome C peroxydase, les glutathion peroxydases, les catalases et les peroxydases simplex.Mention may be made, as oxidoreductases with 2 electrons, of pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases. Mention may be made, as oxidoreductases with 4 electrons, of laccases, tyrosinases, catechol oxidases and polyphenol oxidases. As peroxidases, mention may be made of NADH peroxidases, peroxidase fatty acids, NADPH peroxidases, cytochrome C peroxidase, glutathione peroxidases, catalases and peroxidases simplex.
Le peroxyde d'hydrogène et les systèmes d'oxydations enzymatiques sont particulièrement préférés. La composition oxydante contenant l'agent oxydant peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux et tels que définis précédemment.Hydrogen peroxide and enzymatic oxidation systems are particularly preferred. The oxidizing composition containing the oxidizing agent may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
Le pH de la composition oxydante renfermant l'agent oxydant est tel qu'après mélange avec la composition tinctoriale, le pH de la composition résultante appliquée sur les fibres kératiniques varie de préférence entre 3 et 12 environ, et encore plus prèférentiellement entre 5 et 11. Il peut être ajusté à la valeur désirée au moyen d'agents acidifiants ou alcalinisants habituellement utilisés en teinture des fibres kératiniques et tels que définis précédemment.The pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 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 in dyeing keratin fibers and as defined above.
La composition qui est finalement appliquée sur les fibres kératiniques peut se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques, et notamment des cheveux humains.The composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.
Un autre objet de l'invention est un dispositif à plusieurs compartiments ou "kit" de teinture dans lequel un premier compartiment renferme la composition tinctoriale définie ci-dessus et un deuxième compartiment renferme la composition oxydante. Ce dispositif peut être équipé d'un moyen permettant de délivrer sur les cheveux le mélange souhaité, tel que les dispositifs décrits dans le brevet FR-2 586 913 au nom de la demanderesse.Another object of the invention is a device with several compartments or "kit" for dyeing in which a first compartment contains the dye composition defined above and a second compartment contains the oxidizing composition. This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.
L'invention a également pour objet le produit coloré résultant de la réaction d'au moins un composé de formule (I) telle que définie ci-dessus avec un coupleur en présence d'au moins un agent oxydant tel que défini précédemment.A subject of the invention is also the colored product resulting from the reaction of at least one compound of formula (I) as defined above with a coupler in the presence of at least one oxidizing agent as defined above.
Ces produits colorés peuvent notamment se présenter sous la forme de pigments et être utilisés à titre de colorant direct pour la teinture directe des cheveux ou bien encore être incorporés dans des produits cosmétiques tels que par exemple dans des produits de maquillage.These colored products may in particular be in the form of pigments and be used as direct dye for the direct dyeing of the hair or even be incorporated in cosmetic products such as for example in makeup products.
La présente invention a enfin pour objet des composés nouveaux de formules (I), (la), (Ib), (le) telles que définis précédemment. Les exemples qui suivent servent à illustrer l'invention sans toutefois en limiter la portée. The present invention finally relates to new compounds of formulas (I), (la), (Ib), (le) as defined above. The examples which follow serve to illustrate the invention without however limiting its scope.
EXEMPLESEXAMPLES
EXEMPLE DE SYNTHESEEXAMPLE OF SYNTHESIS
I. Synthèse du di chlorhydrate de N-acetyl (6-méthoxy-2-méthyl-2H- pyridazin-3- ylidene)-hydrazoneI. Synthesis of N-acetyl hydrochloride (6-methoxy-2-methyl-2H- pyridazin-3-ylidene) -hydrazone
Figure imgf000021_0001
Figure imgf000021_0001
MeSO,meSO,
Etape n°1 : Préparation du sel de méthosulfate de 2-methyl-3-chloro-6- méthoxypyridaziniumStep 1: Preparation of the 2-methyl-3-chloro-6-methoxypyridazinium methosulfate salt
Dans un ballon, on a introduit 10 g de 3-chloro-6-méthoxypyridazine (0,069 mol), 26,44 ml de diméthylsulfate (0,279 mol) et 100 ml d'acétate d'éthyle. Le mélange hétérogène à l'origine a été laissé à 45°C pendant 12 heures. Le précipité obtenu est alors filtré puis lavé plusieurs fois à l'acétate d'éthyle. Le solide blanc alors obtenu est séché sous vide en présence de P2O5 ; 16,79 g d'un solide blanc ont été obtenus10 g of 3-chloro-6-methoxypyridazine (0.069 mol), 26.44 ml of dimethyl sulphate (0.279 mol) and 100 ml of ethyl acetate were introduced into a flask. The originally heterogeneous mixture was left at 45 ° C for 12 hours. The precipitate obtained is then filtered and then washed several times with ethyl acetate. The white solid then obtained is dried under vacuum in the presence of P 2 O 5 ; 16.79 g of a white solid were obtained
(rendement 90%).(90% yield).
L'analyse RMN H (D2O d2, 200 MHz, ppm) conforme au produit attendu était la suivante : 8,25 (d, J = 9,6 Hz, 1H) ; 7,82 (d, J = 9,6 Hz, 1 H) ; 4,41 (s, 3H) ; 4,02 (s, 3H) ; 3,60 (s, 3H).H NMR analysis (D 2 O d 2 , 200 MHz, ppm) in accordance with the expected product was as follows: 8.25 (d, J = 9.6 Hz, 1H); 7.82 (d, J = 9.6 Hz, 1H); 4.41 (s, 3H); 4.02 (s, 3H); 3.60 (s, 3H).
L'analyse RMN 13C (D2O d2, 50 MHz, ppm) conforme au produit attendu était la suivante : 165,5 ; 141,3 ; 138,34 ; 130,21 ; 57,31 ; 55,77 ; 51,23The 13 C NMR analysis (D 2 O d 2 , 50 MHz, ppm) in accordance with the expected product was as follows: 165.5; 141.3; 138.34; 130.21; 57.31; 55.77; 51.23
Etape n°2 : Préparation du N-acetyl (6-méthoxy-2-méthyl-2H- pyridazin-3- ylidene)-hydrazone.Step 2: Preparation of N-acetyl (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone.
Dans un ballon, on a introduit 1g du sel de méthosulfate de 2-methyl-3- chloro-6-méthoxypyridazinium (0,0037 mol), 0,6 g d'acétylhydrazine (0,0081 mole), 5 ml de triéthylamine et 10 ml d'éthanol. Le mélange hétérogène à l'origine se décolore très rapidement en orange dès l'ajout de triéthylamine. Celui-ci a été laissé à température ambiante pendant 4 heures. Après avoir concentré le milieu réactionnel, celui-ci est repris avec 10 ml d'une solution saturée en NaCI puis extrait plusieurs fois avec de l'acétate d'éthyle. Le résidu solide orangé obtenu après concentration de la phase organique est ensuite chromatographié sur gel de silice (éluant CH2CI2/EtOH, 90/10 ; Rf : 0.14). 0,51 g d'un solide orange a été obtenu (rendement 70 %).1 g of the 2-methyl-3-chloro-6-methoxypyridazinium methosulfate salt (0.0037 mol), 0.6 g of acetylhydrazine (0.0081 mol), 5 ml of triethylamine and 10 ml of ethanol. The originally heterogeneous mixture discolors very quickly to orange as soon as triethylamine is added. This was left at room temperature for 4 hours. After concentrating the reaction medium, it is taken up in 10 ml of a saturated NaCl solution and then extracted several times with ethyl acetate. The orange-colored solid residue obtained after concentration of the organic phase is then chromatographed on silica gel (eluent CH 2 CI 2 / EtOH, 90/10; Rf: 0.14). 0.51 g of an orange solid was obtained (yield 70%).
L'analyse RMN 1H (CD3OD d4, 200 MHz, ppm) conforme au produit attendu était la suivante : 7,18 (d, J = 10 Hz, 1H) ; 6,86 (d, J = 10 Hz, 1H) ; 3,84 (s, 3H) ; 3,63 (s, 3H) ; 2,06 (s, 3H). L'analyse en FIA/ESI+/7MS conforme au produit attendu était la suivante : M/Z : 197 (M+H)+ Analyse élémentaire:The 1 H NMR analysis (CD 3 OD d 4 , 200 MHz, ppm) in accordance with the expected product was as follows: 7.18 (d, J = 10 Hz, 1H); 6.86 (d, J = 10 Hz, 1H); 3.84 (s, 3H); 3.63 (s, 3H); 2.06 (s, 3H). The analysis in FIA / ESI + / 7MS in accordance with the expected product was as follows: M / Z: 197 (M + H) + Elemental analysis:
Figure imgf000022_0002
Figure imgf000022_0002
H. Synthèse du (6-méthoxy-2-méthyl-2H- pyridazin-3-ylidene)-hydrazoneH. Synthesis of (6-methoxy-2-methyl-2H- pyridazin-3-ylidene) -hydrazone
Figure imgf000022_0001
Figure imgf000022_0001
2 HCI2 HCI
Dans un ballon, on a introduit 7g du N-acetyl (6-méthoxy-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone (0,0357 mol) et 700 ml d'une solution d'HCI 6N. Le mélange homogène a été laissé à reflux pendant 12 heures. Après avoir concentré le milieu réactionnel, un résidu beige est obtenu, celui-ci est repris avec de l'éthanol absolu (quelques millilitres) et de l'acétate d'éthyle. Un précipité est obtenu par filtration. Après séchage sous vide en présence de P2O5, 3,5 g d'un solide blanc pur ont été obtenus (rendement 43 %). L'analyse RMN 1H (DMSO d4, 400 MHz, ppm) conforme au produit attendu était la suivante : 7,96 (d, J = 9,9 Hz, 1 H) ; 7,52 (d, J = 10 Hz, 1H) ; 3,86 (s, 3H) ; 3,76 (s, 3H).7 g of N-acetyl (6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone (0.0357 mol) and 700 ml of a 6N HCl solution were introduced into a flask. The homogeneous mixture was left at reflux for 12 hours. After concentrating the reaction medium, a beige residue is obtained, which is taken up in absolute ethanol (a few milliliters) and ethyl acetate. A precipitate is obtained by filtration. After drying under vacuum in the presence of P 2 O 5 , 3.5 g of a pure white solid were obtained (yield 43%). The 1 H NMR analysis (DMSO d 4 , 400 MHz, ppm) in accordance with the expected product was as follows: 7.96 (d, J = 9.9 Hz, 1 H); 7.52 (d, J = 10 Hz, 1H); 3.86 (s, 3H); 3.76 (s, 3H).
L'analyse en FIA/ESI+/7MS conforme au produit attendu était la suivante : M/Z : 155 (M+H)+ Analyse élémentaireThe analysis in FIA / ESI + / 7MS in accordance with the expected product was as follows: M / Z: 155 (M + H) + Elemental analysis
Figure imgf000023_0001
Figure imgf000023_0001
EXEMPLES DE FORMULATIONSEXAMPLES OF FORMULATIONS
On a préparé les compositions tinctoriales suivantes (teneurs en moles)The following dye compositions were prepared (mole contents)
Figure imgf000023_0002
Figure imgf000023_0002
(*) Support de teinture commun :(*) Common dye support:
- Alcool oléique polyglycérolé à 2 moles de glycérol 4 g- Polyglycerolated oleic alcohol with 2 moles of glycerol 4 g
- Alcool oléique polyglycérolé à 4 moles de glycérol, à 78 % de 5,69 g M.A matières actives (M.A.)- Polyglycerolated oleic alcohol with 4 moles of glycerol, 78% 5.69 g M.A active ingredients (M.A.)
- Acide oléique 3,0 g- Oleic acid 3.0 g
- Aminé oléique à 2 moles d'oxyde d'éthylène vendue sous la 7,0 g dénomination commerciale ETHOMEEN O12 ® par la société- Oleic amine containing 2 moles of ethylene oxide sold under the 7.0 g trade name ETHOMEEN O12 ® by the company
AKZOAKZO
- Laurylamino succinamate de diéthylaminopropyle, sel de sodium 3,0 g M.A. à 55 % de M.A- Laurylamino diethylaminopropyl succinamate, sodium salt 3.0 g M.A. at 55% M.A.
- Alcool oléique 5,0 g - Diéthanolamide d'acide oléique 12,0 g- Oleic alcohol 5.0 g - Oleic acid diethanolamide 12.0 g
- Propylèneglycol 3,5, g- Propylene glycol 3.5, g
- Alcool éthylique 7,0 g- Ethyl alcohol 7.0 g
- Dipropylèneglycol 0,5 g- Dipropylene glycol 0.5 g
- Monométhyléther de propylèneglycol 9,0 g- Propylene glycol monomethyl ether 9.0 g
- Métabisulfite de sodium en solution aqueuse, à 35 % de M.A. 0,455 g M.A- Sodium metabisulfite in aqueous solution, 35% of M.A. 0.455 g M.A
- Acétate d'ammonium 0,8 g- Ammonium acetate 0.8 g
- Antioxydant, séquestrant q.s.- Antioxidant, sequestering q.s.
- Parfum, conservateur q.s.- Perfume, preservative q.s.
- Ammoniaque à 20 % de NH3 10,2 g- Ammonia at 20% NH3 10.2 g
Au moment de l'emploi, chaque composition est mélangée avec un poids égal d'eau oxygénée à 20 volumes (6% en poids).At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight).
Chaque mélange obtenu est appliqué sur des mèches de cheveux gris à 90 % de blancs, permanentes (BP) ou naturels (BN). Après 30 min de pose, les mèches sont rincées, lavées avec un shampooing standard, rincées à nouveau puis séchées. La couleur des mèches a été évaluée dans le système L*a*b*, sur cheveux blancs et permanentes, au moyen d'un spectrophotomètre CM 2002 MINOLTA. Dans l'espace L*a*b*, la clarté est indiquée par la valeur L* sur une échelle de 0 à 100 alors que les coordonnées chromatiques sont exprimées par a* et b* qui indiquent deux axes de couleur, a* l'axe rouge-vert et b* l'axe jaune- bleu.Each mixture obtained is applied to locks of gray hair containing 90% white, permanent (BP) or natural (BN). After 30 min of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The color of the locks was evaluated in the L * a * b * system, on white and permanent hair, using a CM 2002 MINOLTA spectrophotometer. In space L * a * b *, clarity is indicated by the value L * on a scale from 0 to 100 while the chromatic coordinates are expressed by a * and b * which indicate two axes of color, a * l 'red-green axis and b * yellow-blue axis.
Selon ce système, plus la valeur de L est élevée, plus la couleur est claire et peu intense. Inversement, plus la valeur de L est faible, plus la couleur est foncée ou très intense. According to this system, the higher the value of L, the lighter and less intense the color. Conversely, the lower the value of L, the darker or very intense the color.
Figure imgf000025_0001
Figure imgf000025_0001
(- non disponible)(- not available)
EXEMPLES 4 A 10 DE TEINTUREEXAMPLES 4 TO 10 OF DYEING
On prépare les compositions tinctoriales suivantes (mole)The following dye compositions are prepared (mole)
Figure imgf000025_0002
Figure imgf000025_0002
(1) préparé selon la synthèse de l'exemple 1 à partir de 3-chloro 6-pyrrolidin-N-yl-pyridazine ; (2) préparé selon la synthèse de l'exemple 1 à partir de 3-chloro 6-phénylpyrazine.(1) prepared according to the synthesis of Example 1 from 3-chloro 6-pyrrolidin-N-yl-pyridazine; (2) prepared according to the synthesis of Example 1 from 3-chloro 6-phenylpyrazine.
(*) Support de teinture (1 ) pH 9,5(*) Dye medium (1) pH 9.5
Alcool éthylique à 96° 20 gEthyl alcohol at 96 ° 20 g
Métabisulfite de sodium en solution aqueuse à 35% 0,2275g M.ASodium metabisulfite in 35% aqueous solution 0.22275g M.A
Sel pentasodique de l'acide diethylene triamino pentacétique 0,48g M.ADiethylene triamino pentacetic acid pentasodium salt 0.48g M.A
Alkyl en C8-C,5polyglucoside vendu en solution à 60% sous la dénomination ORAMIXCG110 par la société SEPPICC 8 -C 5 alkyl polyglucoside sold in 60% solution under the name ORAMIXCG110 by the company SEPPIC
3,6g M.A Alcool benzylique 2,0g3.6g MA Benzyl alcohol 2.0g
Polyethylène glycol à 8 moles d'OE 3,0gPolyethylene glycol with 8 moles of EO 3.0g
NH4CI 4,28gNH 4 CI 4.28g
Ammoniaque à 20% de NH3 6,8 gAmmonia at 20% NH3 6.8 g
(*) Support de teinture (2) pH 7(*) Dye medium (2) pH 7
Alcool éthylique à 96° 20 gEthyl alcohol at 96 ° 20 g
Métabisulfite de sodium en solution aqueuse à 35% 0,2275g M.ASodium metabisulfite in 35% aqueous solution 0.22275g M.A
Sel pentasodique de l'acide diethylene triamino 0,48g M.A pentacétiqueDiethylene triamino acid pentasodium salt 0.48g pentacetic M.A
Alkyl en C8-C,5polyglucoside vendu en solution à 60% sous 3,6g M.A la dénomination ORAMIXCG110 par la société SEPPIC C8 alkyl, 5 polyglucoside sold 60% solution under the name 3.6 g MA ORAMIXCG110 by the company SEPPIC
Alcool benzylique 2,0gBenzyl alcohol 2.0g
Polyethylène glycol à 8 moles d'OE 3,0 gPolyethylene glycol with 8 moles of EO 3.0 g
K2HPO4 20,9 gK 2 HPO 4 20.9 g
KH2PO4 10,88gKH 2 PO 4 10.88g
Au moment de l'emploi, chaque composition est mélangée avec un poids égal d'eau oxygénée à 20 volumes (6% en poids). On obtient un pH final de 7 avec la support de teinture (2) et un pH 9.5 avec la support de teinture (1).At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained with the dye support (2) and a pH 9.5 with the dye support (1).
Chaque mélange obtenu est appliqué sur des mèches de cheveux gris à 90 % de blancs. Après 30 min de pose, les mèches sont rincées, lavées avec un shampooing standard, rincées à nouveau puis séchées.Each mixture obtained is applied to locks of gray hair containing 90% white hairs. After 30 min of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
Les résultats de teinture suivants ont été obtenus.The following dye results were obtained.
Figure imgf000026_0001
Figure imgf000026_0001

Claims

REVENDICATIONS
1. Composition tinctoriale pour la teinture de fibres kératiniques comprenant dans un milieu approprié pour la teinture de ces fibres, • à titre de base d'oxydation, au moins un composé du type hydrazone de formule (I) suivante ou le sel d'addition avec un acide ou une base correspondant1. Dye composition for dyeing keratin fibers comprising, in an appropriate medium for dyeing these fibers, • as oxidation base, at least one compound of the hydrazone type of formula (I) below or the addition salt with a corresponding acid or base
W ^XW ^ X
™ d) dans laquelle™ d) in which
- X représente un atome d'azote ou CR2 ; Y représente un atome d'azote ou CR3 ; Z représente un atome d'azote ou CR4 et W représente un atome d'azote ou- X represents a nitrogen atom or CR2; Y represents a nitrogen atom or CR3; Z represents a nitrogen atom or CR4 and W represents a nitrogen atom or
CR5 ;CR 5 ;
- A représente un atome d'hydrogène ; un radical acyle , un radical alkylsulfonyle en C,-C4 ou un radical arylsulfonyle, ces radicaux étant éventuellement substitués par un méthyl, un alkoxy en C,-C2 ou un carboxyl, - R, représente une chaîne carbonée en C,-C„, saturée ou pouvant contenir une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples, linéaire ou ramifiée pouvant former un cycle ayant de 3 à 6 chaînons, éventuellement aromatique, un ou plusieurs atomes de carbone de la chaîne pouvant être remplacés par un atome d'oxygène, d'azote, d'halogène ou de soufre ou par un groupe SO2 à l'exception du carbone lié à l'atome d'azote; le radical R, ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;- A represents a hydrogen atom; an acyl radical, a C 4 -C 4 alkylsulfonyl radical or an arylsulfonyl radical, these radicals being optionally substituted by a methyl, a C 2 -C 2 alkoxy or a carboxyl, - R, represents a carbon chain at C, - C „, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may form a ring having 3 to 6 members, optionally aromatic, one or more carbon atoms of the chain which may be replaced by an oxygen, nitrogen, halogen or sulfur atom or by an SO 2 group with the exception of the carbon bonded to the nitrogen atom; the radical R, comprising no peroxide bond, nor diazo, nitro or nitroso radicals;
- R2, R3, R4 et R5 représentent, chacun séparément un atome d'hydrogène ; un radical alkyle ou alcényle en C,-C,2, linéaire ou ramifié ou sous forme de cycle carboné ayant de 3 à 6 chaînons, éventuellement aromatique ; un ou plusieurs atomes de carbone des radicaux alkyle ou alcényle pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote ou de soufre, par un groupement SO2, avec les conditions suivantes- R 2 , R 3 , R 4 and R 5 each represent a hydrogen atom separately; a linear or branched C 1 -C 2 alkyl or alkenyl radical or in the form of a carbon ring having 3 to 6 members, optionally aromatic; one or more carbon atoms of the alkyl or alkenyl radicals which can be replaced by one or more oxygen, nitrogen or sulfur atoms, by an SO 2 group, with the following conditions
- un des groupes X, Y, W et Z représente un atome d'azote,one of the groups X, Y, W and Z represents a nitrogen atom,
- lorsque X = N, alors Y = CR3 et Z = CR4 et W ≈ CR5, - lorsque Z = N, alors X = CR2 et Y = CR3 et W = CR5,- when X = N, then Y = CR 3 and Z = CR 4 and W ≈ CR 5 , - when Z = N, then X = CR 2 and Y = CR 3 and W = CR 5 ,
- lorsque W = N, alors X = CR2 et Y = CR3 et Z = CR4,- when W = N, then X = CR 2 and Y = CR 3 and Z = CR 4 ,
- lorsque Y = N, alors X = CR2 et Z = CR4 et W = CR5 et avec les conditions supplémentaires suivantes : si X = N, Y = CR3, Z = CR4 et W = CR5, alors le groupe R4 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde , si Z = N, X = CR2, Y = CR3 et W = CR5, alors le groupe R2 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde, si W = N, X = CR2, Y = CR3 et Z = CR4, alors le groupe R3 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde, si Y = N, X = CR2, Z = CR4 et W = CR5, alors le groupe R5 est différent d'un radical alkylsulfonyle, arylsulfonyle, alkylsulfoxyde ou arylsulfoxyde, et- when Y = N, then X = CR 2 and Z = CR 4 and W = CR 5 and with the following additional conditions: if X = N, Y = CR 3 , Z = CR 4 and W = CR 5 , then the group R 4 is different from an alkylsulfonyl, arylsulfonyl, alkylsulfoxide or arylsulfoxide radical, if Z = N, X = CR 2 , Y = CR 3 and W = CR 5 , then the R 2 group is different from an alkylsulfonyl radical, arylsulfonyl, alkylsulfoxide or arylsulfoxide, if W = N, X = CR 2 , Y = CR 3 and Z = CR 4 , then the group R 3 is different from an alkylsulfonyl, arylsulfonyl, alkylsulfoxide or arylsulfoxide radical, if Y = N, X = CR 2 , Z = CR 4 and W = CR 5 , then the group R 5 is different from an alkylsulfonyl, arylsulfonyl, alkylsulfoxide or arylsulfoxide radical, and
• au moins un coupleur ou le sel d'addition avec un acide correspondant.• at least one coupler or the addition salt with a corresponding acid.
2. Composition selon la revendication 1 dans laquelle A représente l'hydrogène ; un radical acyle ; un radical méthylsulfonyle ; un radical phényisulfonyle ; un radical toluylsulfonyle.2. Composition according to claim 1 in which A represents hydrogen; an acyl radical; a methylsulfonyl radical; a phenyisulfonyl radical; a toluylsulfonyl radical.
3. Composition selon la revendication 1 ou 2 dans laquelle R, représente un radical alkyle ou alcényle en C,-C4 pouvant être substitué par un ou plusieurs substituants hydroxy, amino éventuellement substitué, carboxy^ un radical phényle, pouvant être substitué par un ou plusieurs atomes d'halogène, groupes alkyle en C,-C4, alcoxy en C,-C4, amino, hydroxy, trifluorométhyle, alkylamino en C,-C4, carboxy, sulfonyle ; un radical benzyle pouvant être substitué par un ou plusieurs atomes d'halogène, groupes alkyle en C,-C4, alcoxy en C,-C4, amino, hydroxy, trifluorométhyle, alkylamino en C,-C4, carboxy, sulfonyle ; un radical alkylamino en C,- C4 ; un hétérocycle choisi parmi l'imidazole, le thiazole, la pyridine ou la pyrimidine ; un radical (CH2)p-T-(CH2)q-VR' où p et q sont entiers, identiques ou différents, compris entre 1 et 3, R' représente H ou méthyle et T et V désignent indépendamment un atome d'oxygène ou un radical NR" avec R" désignant un hydrogène ou un méthyle.3. Composition according to claim 1 or 2 in which R represents a C 4 -C 4 alkyl or alkenyl radical which may be substituted by one or more hydroxy, optionally substituted amino substituents, carboxy ^ a phenyl radical, which may be substituted by a or more halogen atoms, alkyl C, -C 4 alkoxy, C, -C 4 alkyl, amino, hydroxy, trifluoromethyl, alkylamino, C, -C 4 alkyl, carboxy, sulfonyl; benzyl which may be substituted by one or more halogen atoms, alkyl C, -C 4 alkoxy, C, -C 4 alkyl, amino, hydroxy, trifluoromethyl, alkylamino, C, -C 4 alkyl, carboxy, sulfonyl; a C 1 -C 4 alkylamino radical; a heterocycle chosen from imidazole, thiazole, pyridine or pyrimidine; a radical (CH2) p -T- (CH2) q -VR 'where p and q are whole, identical or different, comprised between 1 and 3, R' represents H or methyl and T and V independently denote an oxygen atom or a radical NR "with R" denoting hydrogen or methyl.
4. Composition selon la revendication 3 dans laquelle R, représente un radical méthyle ; éthyle ; isopropyle , hydroxyéthyle ; aminoéthyle ; carboxyméthyle ; carboxyéthyle ; phényle ; 2-méthoxyphényle ; 3-méthoxyphényle ; 4-méthoxyphényle ; 2-hydroxyphényle ; 3-hydroxyphényle ; 4-hydroxyphényle ; benzyle ; les hétérocycles choisi parmi pyridyle, imidazolyle, pyrimidinyle. 4. Composition according to claim 3 in which R represents a methyl radical; ethyl; isopropyl, hydroxyethyl; aminoethyl; carboxymethyl; carboxyethyl; phenyl; 2-methoxyphenyl; 3-methoxyphenyl; 4-methoxyphenyl; 2-hydroxyphenyl; 3-hydroxyphenyl; 4-hydroxyphenyl; benzyl; heterocycles chosen from pyridyle, imidazolyle, pyrimidinyle.
5. Composition selon la revendication 4 dans laquelle R1 représente un méthyle ; éthyle ; phényle ; 2-méthoxyphényl ; 2-hydroxyphényl ; hydroxyéthyle ; aminoéthyle ; carboxyéthyle.5. Composition according to claim 4 in which R1 represents a methyl; ethyl; phenyl; 2-methoxyphenyl; 2-hydroxyphenyl; hydroxyethyl; aminoethyl; carboxyethyl.
6. Composition selon l'une quelconque des revendications précédentes dans laquelle R2, R3, R4 et R5 représentent un atome d'hydrogène ; un radical alkyle pouvant être substitué par un hydroxy, amino ou halogène ; un radical phényle éventuellement substitué par un ou plusieurs substituants choisis parmi les radicaux alkyle, hydroxy, amino, alcoxy, carboxy, trifluorométhyle, sulfonique ; un benzyle pouvant être substitué par un alcoxy ou hydroxy ; un hétérocycle choisi parmi N- pyrrolidinyle, N-pipéridinyle, N-morpholine, N-pipérazinyle ou N-imidazolyle ; un radical alcoxy ; un radical phosphonyle ; un radical siloxy ; un radical amino ; un radical acyle ; un radical acylamino ; un radical sulfonamide ; un radical uréido ; un radical sulfonylamino.6. Composition according to any one of the preceding claims, in which R 2 , R 3 , R 4 and R 5 represent a hydrogen atom; an alkyl radical which may be substituted by hydroxy, amino or halogen; a phenyl radical optionally substituted by one or more substituents chosen from alkyl, hydroxy, amino, alkoxy, carboxy, trifluoromethyl, sulfonic radicals; a benzyl which can be substituted by an alkoxy or hydroxy; a heterocycle chosen from N-pyrrolidinyl, N-piperidinyl, N-morpholine, N-piperazinyl or N-imidazolyl; an alkoxy radical; a phosphonyl radical; a siloxy radical; an amino radical; an acyl radical; an acylamino radical; a sulfonamide radical; a ureido radical; a sulfonylamino radical.
7. Composition selon la revendication 6 dans laquelle R2, R3, R4 et R5 représentent l'hydrogène ; un radical alkyle choisi parmi méthyle, éthyle ; un radical alkyl substitué choisis parmi trifluorométhyle, hydroxyméthyle, hydroxyéthyle, aminométhyle, aminoéthyle ; le benzyle ; un phényl éventuellement substitué par un ou plusieurs radicaux choisi dans le groupe constitué des radicaux méthyl, hydroxy, aminé, méthoxy ; 2-méthoxybenzyle ; 4-méthoxybenzyle ; 2-hydroxybenzyle ; 4- hydroxybenzyle ; un hétérocycle choisi parmi pyrrolidinyle, pipéridinyle ; un radical méthoxy ; un radical acyle ; un radical amino.7. Composition according to claim 6 in which R 2 , R 3 , R 4 and R 5 represent hydrogen; an alkyl radical chosen from methyl, ethyl; a substituted alkyl radical chosen from trifluoromethyl, hydroxymethyl, hydroxyethyl, aminomethyl, aminoethyl; benzyl; a phenyl optionally substituted by one or more radicals chosen from the group consisting of methyl, hydroxy, amino, methoxy radicals; 2-methoxybenzyl; 4-methoxybenzyl; 2-hydroxybenzyl; 4- hydroxybenzyl; a heterocycle chosen from pyrrolidinyl, piperidinyl; a methoxy radical; an acyl radical; an amino radical.
8. Composition selon la revendication 7 dans laquelle R2 R3, R4 et R5 représentent l'hydrogène ; méthyle ; éthyle ; trifluorométhyle ; phényle ; pyrrolidinyle ; hydroxyméthyle ; hydroxyéthyle ; aminométhyle ; aminoéthyle ; méthoxy ; amino. 8. Composition according to Claim 7, in which R 2 R 3 , R 4 and R 5 represent hydrogen; methyl; ethyl; trifluoromethyl; phenyl; pyrrolidinyl; hydroxymethyl; hydroxyethyl; aminomethyl; aminoethyl; methoxy; amino.
9. Composition selon l'une quelconque des revendications précédentes dans laquelle le composés de formule (I) présentent l'une des formules suivantes9. Composition according to any one of the preceding claims, in which the compounds of formula (I) have one of the following formulas
Figure imgf000029_0001
dans lesquelles les groupes R,, R2, R3, R4, R5 et A sont tels que définis à l'une quelconque des revendications 1 à 8.
Figure imgf000029_0001
in which the groups R ,, R 2 , R 3 , R 4 , R 5 and A are as defined in any one of Claims 1 to 8.
10. Composition selon l'une quelconque des revendications précédentes dans laquelle la base d'oxydation de type hydrazone correspond à la formule suivante10. Composition according to any one of the preceding claims, in which the hydrazone-type oxidation base corresponds to the following formula.
Figure imgf000030_0001
dans laquelle R1 , A, R2, R4 et R5 sont tels que définis précédemment.
Figure imgf000030_0001
in which R1, A, R2, R4 and R5 are as defined above.
11. Composition selon la revendication 10 dans laquelle R1 est un radical alkyle, A, R2 et R4 sont l'hydrogène, et R5 est un radical alcoxy, phényle ou pyrrolidine.11. Composition according to claim 10, in which R1 is an alkyl radical, A, R2 and R4 are hydrogen, and R5 is an alkoxy, phenyl or pyrrolidine radical.
12. Composition selon la revendication 11 dans laquelle le composé hydrazone est choisi parmi 6-méthoxy-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone, 6- (pyrrolidin-N-yl)-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone, 6-phényl-2-méthyl-2H- pyridazin-3-ylidene)-hydrazone. 12. Composition according to claim 11 in which the hydrazone compound is chosen from 6-methoxy-2-methyl-2H-pyridazin-3-ylidene) -hydrazone, 6- (pyrrolidin-N-yl) -2-methyl-2H- pyridazin-3-ylidene) -hydrazone, 6-phenyl-2-methyl-2H- pyridazin-3-ylidene) -hydrazone.
13. Composition selon l'une quelconque des revendications précédentes dans laquelle le coupleur est choisi parmi les métaphénylènediamines, les méta- aminophénols, les métadiphénols et les coupleurs hétérocycliques.13. Composition according to any one of the preceding claims, in which the coupler is chosen from metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers.
14. Composition selon l'une quelconque des revendications précédentes dans laquelle le ou les composés de formule (I) sont chacun présents en quantité comprise entre 0,001 et 10 %, et le ou les coupleurs sont présents en quantité comprise entre 0,001 et 10 % en poids du poids total de la composition tinctoriale.14. Composition according to any one of the preceding claims, in which the compound or compounds of formula (I) are each present in an amount of between 0.001 and 10%, and the coupler (s) are present in an amount of between 0.001 and 10%. weight of the total weight of the dye composition.
15. Composition selon l'une quelconque des revendications 1 à 14 conmprenant de plus une base d'oxydation additionnelle choisie parmi les paraphénylènediamines, les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols, les bases hétérocycliques, et leurs sels d'addition avec un acide.15. Composition according to any one of claims 1 to 14 further comprising an additional oxidation base chosen from paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and their salts d 'addition with an acid.
16. Composition selon la revendication 15, dans laquelle la base d'oxydation additionnelle est présente en quantité comprise entre 0,001 et 10 %, de préférence entre 0,005 et 6 % en poids du poids total de la composition tinctoriale.16. Composition according to claim 15, in which the additional oxidation base is present in an amount between 0.001 and 10%, preferably between 0.005 and 6% by weight of the total weight of the dye composition.
17. Composition selon l'une quelconque des revendications 1 à 16 comprenant de plus un colorant direct.17. Composition according to any one of claims 1 to 16 further comprising a direct dye.
18. Procédé de teinture d'oxydation des fibres kératiniques caractérisé en ce qu'on applique sur les fibres au moins une composition telle que définie à l'une quelconque des revendications 1 à 17, et qu'on révèle la couleur à l'aide d'un agent oxydant.18. Process for the oxidation dyeing of keratinous fibers, characterized in that at least one composition as defined in one is applied to the fibers any of claims 1 to 17, and the color is revealed using an oxidizing agent.
19. Procédé selon la revendication 18 dans lequel l'agent oxydant est choisi parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bramâtes de métaux alcalins, les persels, les peracides et les systèmes d'oxydation enzymatique.19. The method of claim 18 wherein the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bramates, persalts, peracids and enzymatic oxidation systems.
20. Procédé selon la revendication 19 dans lequel le système d'oxydation enzymatique est choisi parmi les peroxydases en présence d'au moins un donneur pour ces peroxydases, les oxydoréductases à 2 électrons en présence d'au moins un donneur pour ces oxydoréductases, et les oxydoréductases à 4 électrons. 20. The method of claim 19 wherein the enzymatic oxidation system is chosen from peroxidases in the presence of at least one donor for these peroxidases, 2-electron oxidoreductases in the presence of at least one donor for these oxidoreductases, and 4-electron oxidoreductases.
21. Procédé selon l'une des revendications 18 à 20 dans lequel l'agent oxydant est mélangé au moment de Femploi à la composition telle que définie selon l'une quelconque des revendications 1 à 17.21. Method according to one of claims 18 to 20 in which the oxidizing agent is mixed at the time of use with the composition as defined according to any one of claims 1 to 17.
22. Procédé selon l'une quelconque des revendications 18 à 20 dans lequel l'agent oxydant est appliqué sous forme de composition oxydante simultanément ou séquentiellement à la composition telle que définie selon l'une quelconque des revendications 1 à 17 sur les fibres.22. Method according to any one of claims 18 to 20 in which the oxidizing agent is applied in the form of an oxidizing composition simultaneously or sequentially to the composition as defined according to any one of claims 1 to 17 on the fibers.
23. Dispositif à plusieurs compartiments ou "kit" de teinture à plusieurs compartiments, dans lequel un premier compartiment contient une composition telle que définie à l'une quelconque des revendications 1 à 17 et un deuxième compartiment contient un agent oxydant.23. Multi-compartment device or multi-compartment dye "kit", in which a first compartment contains a composition as defined in any one of claims 1 to 17 and a second compartment contains an oxidizing agent.
24. Produit coloré susceptible d'être obtenu par réaction d'au moins un composé de formule (I) et un coupleur tels que définis dans l'une quelconque des revendications 1 à 17 et au moins un agent oxydant.24. Colored product capable of being obtained by reaction of at least one compound of formula (I) and a coupler as defined in any one of claims 1 to 17 and at least one oxidizing agent.
25. Nouveaux composés de formules (I), (la), (Ib) (le) telles que définies selon l'une quelconque des revendications 1 à 12 . 25. New compounds of formulas (I), (la), (Ib) (le) as defined according to any one of claims 1 to 12.
PCT/FR2002/000856 2001-03-15 2002-03-11 Novel dyeing compositions for the dyeing of keratin fibres comprising 6-membered heterocyclic hydrazone compounds as an oxidation base WO2002074267A1 (en)

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FR0103539A FR2822063B1 (en) 2001-03-15 2001-03-15 NOVEL TINCTORIAL COMPOSITIONS FOR DYEING KERATIN FIBERS COMPRISING THE BASIS FOR OXIDATION OF 6-CHAIN HETEROCYCLIC HYDRAZONE COMPOUNDS

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004078151A1 (en) * 2003-03-05 2004-09-16 Wella Aktiengesellschaft Means and method for dyeing keratin fibres
US7294151B2 (en) 2003-03-05 2007-11-13 Wella Ag Means and method for dyeing keratin fibres

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