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WO2018104474A1 - Composé dérivé de 4,5-diaminopyrazoles comprenant un cycle fusionné, composition comprenant au moins un tel composé, procédé de mise en oeuvre et utilisation - Google Patents

Composé dérivé de 4,5-diaminopyrazoles comprenant un cycle fusionné, composition comprenant au moins un tel composé, procédé de mise en oeuvre et utilisation Download PDF

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Publication number
WO2018104474A1
WO2018104474A1 PCT/EP2017/081881 EP2017081881W WO2018104474A1 WO 2018104474 A1 WO2018104474 A1 WO 2018104474A1 EP 2017081881 W EP2017081881 W EP 2017081881W WO 2018104474 A1 WO2018104474 A1 WO 2018104474A1
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radical
compound
chosen
alkyl
tetrahydropyrazo
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PCT/EP2017/081881
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English (en)
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Aziz Fadli
Zhibo LIU
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L'oreal
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Publication of WO2018104474A1 publication Critical patent/WO2018104474A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • 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

Definitions

  • the present invention relates to compounds of formula (I), derived from 4,5- diaminopyrazoles comprising a fused ring, and also to the use thereof for dyeing keratin fibres, in particular human keratin fibres such as the hair, in the presence of an oxidizing agent.
  • oxidation dye precursors which are generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols, or heterocyclic compounds such as pyrazoles, pyrazolinones or pyrazolo-pyridines.
  • oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, may give rise to coloured compounds via a process of oxidative condensation.
  • oxidation bases may be varied by combining them with couplers or colour modifiers, the latter being chosen especially from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole or pyridine compounds.
  • couplers or colour modifiers the latter being chosen especially from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole or pyridine compounds.
  • couplers or colour modifiers the variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.
  • the oxidation dyeing process thus consists in applying to keratin fibres a dyeing composition comprising oxidation bases or a mixture of oxidation bases and couplers with hydrogen peroxide (H2O2 or aqueous hydrogen peroxide solution), as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres.
  • a dyeing composition comprising oxidation bases or a mixture of oxidation bases and couplers with hydrogen peroxide (H2O2 or aqueous hydrogen peroxide solution), as oxidizing agent
  • the use of these dyeing compositions still has a certain number of drawbacks. Specifically, after application to keratin fibres, the dyeing power obtained may not be entirely satisfactory, or may even be weak, and lead to a restricted range of colours.
  • the colourings may also be insufficiently persistent with respect to external agents such as light, shampoo or perspiration, and may also be too selective, i.e. the difference in colouring is too great along the same keratin fibre that is differently sensitized between its end and its root.
  • dyes are sought which give chromatic and/or intense shades to the hair.
  • compositions for oxidation dyeing comprising diaminopyrazole derivatives and couplers of the meta-phenylenediamine, meta-aminophenol or benzoxazine type are also known in patent applications EP 873 109, EP 871 426 and EP 692 245.
  • compositions do not make it possible to meet all the above- mentioned requirements, in particular in terms of build-up, chromaticity, fastness with respect to washing, to light and/or to sweat, and/or selectivity of the colouring between the root and the end.
  • a subject of the invention is thus a compound of formula (I) below, and also the tautomeric forms, optical isomers and geometrical isomers thereof, the addition salts thereof with an organic or mineral acid or base, and/or the solvates thereof:
  • Ci-Cio alkyl or C2-C10 alkenyl or C2-C10 alkynyl radical optionally interrupted with one or more non-adjacent heteroatoms or groups chosen from O, N(Ra), S and C(O), and/or optionally substituted with one or more radicals, which may be identical or different, chosen from the radicals -OR 4 , -SR 4 , -NRaRb, -C(0)-0-R 4 and -C(0)-NRaR b ,
  • R2 and R3, which may be identical or different, represent a hydroxyl radical, or a Ci- C 6 alkyl or C3-C7 cycloalkyl radical, optionally interrupted with one or more non- adjacent heteroatoms or groups chosen from O, N(Ra), S and C(O), and/or optionally substituted with one or more radicals, which may be identical or different, chosen from -OR 4 , -SR 4 , -NRaRb, -C(0)-OR 4 and -C(0)-NRaR b ;
  • R2 and R3 form, with the carbon atom which bears them:
  • R 4 represents a hydrogen atom or a linear or branched Ci-C 6 alkyl radical, or a C 4 -C 7 cycloalkyl radical;
  • Ra and Rb which may be identical or different, represent a hydrogen atom or a linear or branched Ci-C 6 alkyl radical, or a C 5 -C 7 cycloalkyl radical,
  • Ra and Rb form, with the nitrogen atom which bears them, a 3- to 8-membered heterocycle optionally containing one or more non-adjacent heteroatoms chosen from O, N(Ra) and S, said ring being optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical or a Ci-C 6 (hydro xy)alkyl radical.
  • the compounds of formula (I) according to the invention can thus give colourings that are resistant to the various attacking factors to which keratin fibres may be subjected, such as inclement weather, light, washing and perspiration.
  • the compounds of formula (I) according to the invention can satisfactorily dye keratin fibres, especially producing powerful, chromatic and sparingly selective colourings, and/or with good colour build-up.
  • the present invention also relates to a cosmetic composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising one or more compounds of formula (I) as defined previously, and/or the tautomeric forms, optical isomers and geometrical isomers thereof, the addition salts thereof with an organic or mineral acid or base, and/or the solvates thereof.
  • the invention also relates to a ready-to-use composition based on said cosmetic composition according to the invention, for dyeing keratin fibres, in particular human keratin fibres such as the hair, and at least one oxidizing agent.
  • the invention also relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said cosmetic dyeing composition according to the invention is applied to said fibres in the presence of an oxidizing agent.
  • the present invention relates to a process for preparing the compounds of formula (I) as defined previously.
  • a subject of the present invention is also a multi-compartment device for performing the process in accordance with the invention.
  • Another subject of the present invention relates to the use of one or more compound(s) of formula (I), as defined previously, and also the tautomeric forms, optical isomers and geometrical isomers thereof, the addition salts thereof with an organic or mineral acid or base, and/or the solvates thereof, optionally in the presence of one or more additional oxidation base(s) different from the compounds of formula (I), and/or of one or more coupling agent(s), and/or of one or more oxidizing agent(s), for dyeing keratin fibres, in particular human keratin fibres such as the hair.
  • alkyl is intended to mean a linear or branched hydrocarbon-based radical, preferably of Ci-C 6 ;
  • alkenyl is intended to mean a radical comprising from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, better still from 2 to 4 carbon atoms, and containing at least one double bond, preferably between 1 and 3 double bonds, which may be conjugated or non-conjugated, such as ethylenyl;
  • hydroxyalkyl is intended to mean an alkyl group as defined previously substituted with one or more hydroxyl groups, preferably a Ci-C 6 alkyl group substituted with a hydroxyl group, such as hydroxyethyl;
  • (hydroxy)alkyl is intended to mean an alkyl or hydroxyalkyl group as defined previously;
  • alkoxy is intended to mean an -O-alkyl group with alkyl as defined previously;
  • organic or mineral acid salt is intended to mean cosmetically acceptable salts, more particularly salts derived i) from mineral acids and from halogenated acids such as the salts of hydrochloric acid HC1, hydrobromic acid HBr, sulfuric acid H2SO4, ii) from (Ci-C6)alkylsulfonic acids: Alk-S(0) 2 OH such as methanesulfonic acid and ethanesulfonic acid; iii) from arylsulfonic acids: Ar-S(0) 2 OH with Ar representing an aryl group, in particular phenyl group, such as salts derived from benzenesulfonic acid and toluenesulfonic acid; iv) from (poly)(hydroxy)(Ci-C6)alkylcarboxylic acids such as the salts of citric acid; of succinic acid; of tartaric acid; of lactic acid, x) from (Ci-C6)alkylcarboxylic acids such as the salt
  • C 6 )alkoxysulfinic acids Alk-0-S(0)OH such as methoxysulfinic acid and ethoxysulfinic acid; iv) from aryloxysulfinic acids such as to lueneoxy sulfuric acid and phenoxysulfmic acid; vi) from phosphorus-containing acid, such as phosphoric acid H3PO4; v) from (Ci-C6)alkylcarboxylic acids such as acetic acid CH3C(0)OH; xiv) from triflic acid CF3SO3H and vii) from tetrafluoroboric acid
  • HBF 4 and, preferably, HC1, HBr, H 2 SC"4, H3PO4, or organic acids such as, for example, acetic, lactic, tartaric, citric or succinic acid, benzenesulfonic acid, para-toluenesulfonic acid, formic acid or methanesulfonic acid.
  • organic acids such as, for example, acetic, lactic, tartaric, citric or succinic acid, benzenesulfonic acid, para-toluenesulfonic acid, formic acid or methanesulfonic acid.
  • the compounds of formula (I) may be in the form of solvates, for example a hydrate or a solvate of a linear or branched alcohol such as ethanol or isopropanol.
  • Ri preferably represents:
  • radicals -OR4 a linear or branched C1-C10 alkyl radical, optionally substituted with one or more radicals, which may be identical or different, chosen from the radicals -OR4,
  • C1-C10 preferably Ci-C 6 , better still C1-C4, alkyl radical, such as a methyl or tert-butyl radical,
  • Ri represents a hydrogen atom or a linear or branched C1-C4 alkyl radical, such as a methyl or tert-butyl radical.
  • R 2 and R3 which may be identical or different, represent a Ci-C 6 alkyl or C4-C6 cycloalkyl radical, optionally substituted with one or more hydroxyl radicals, or R 2 and R3 form, with the carbon atom which bears them:
  • ring optionally containing one or more non-adjacent heteroatoms chosen from O, N(Ra) and S, said ring being optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical or a Ci-C 6 (hydroxy)alkyl radical.
  • R 2 and R3 which may be identical or different, represent a Ci-C 6 alkyl or C5-C6 cycloalkyl radical, optionally substituted with one or more hydroxyl radicals, or R 2 and R3 form, with the carbon atom which bears them:
  • ring in particular 4-membered ring, optionally containing one or more non-adjacent heteroatoms chosen from O and N(Ra), in particular containing an oxygen atom, said ring being optionally substituted with one or more Ci-C 6 (hydro xy)alkyl radicals, which may be identical or different, said ring preferably being non-substituted.
  • R 2 and R3 are identical.
  • R 2 and R3 are different.
  • R 2 and R3 which may be identical or different, represent a Ci-C 6 alkyl radical or a Ci-C 6 (hydroxy)alkyl radical.
  • R 2 and R3 denote a radical chosen from methyl, ethyl, hydroxymethyl and hydroxyethyl radicals, better still from methyl and ethyl radicals.
  • R 4 represents a hydrogen atom or a linear or branched Ci-C 6 alkyl radical, or a C5-C6 cycloalkyl radical, and more particularly a hydrogen atom or a linear or branched Ci-C 6 alkyl radical, such as an ethyl radical.
  • Ra and Rb which may be identical or different, represent a hydrogen atom or a linear or branched Ci-C 6 alkyl radical, or a C5-C6 cycloalkyl radical, or Ra and Rb form, with the nitrogen atom which bears them, a 4- to 8- membered heterocycle optionally containing one or more non-adjacent heteroatoms chosen from O and N(Ra), said ring being optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical or a Ci-C 6 (hydroxy)alkyl radical.
  • the compounds correspond to formula (I), in which:
  • Ci-Cio preferably Ci-C 6 , better still C1-C4, alkyl radical, such as a methyl or tert-butyl radical,
  • radical -C(0)-0-R4 such as an ethyl carboxylate radical
  • R2 and R3 which may be identical or different, represent a Ci-C 6 alkyl or C5- C 6 cycloalkyl radical, optionally substituted with one or more hydroxyl radicals, or
  • R 2 and R3 form, with the carbon atom which bears them:
  • ring in particular 4-membered ring, optionally containing one or more non-adjacent heteroatoms chosen from O and N(Ra), in particular containing an oxygen atom, said ring being optionally substituted with one or more Ci-C 6 (hydroxy)alkyl radicals, which may be identical or different, said ring preferably being non-substituted; and
  • R 4 represents a linear or branched Ci-C 6 alkyl radical, such as an ethyl radical.
  • the compounds of formula (I) according to the invention are chosen from the following compounds and the geometrical or optical isomer forms thereof, the tautomers thereof, the addition salts thereof with an organic or mineral acid or base, or the solvates thereof such as hydrates:
  • Ri denotes a hydrogen atom and the other groups R 2 , R3, R4, Ra and Rb have the same meanings as those set out above.
  • the compounds of formula (I) are chosen from the compounds (1) to (6), and also the addition salts thereof, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the solvates thereof, and mixtures thereof.
  • the compound of formula (I) is the compound (1).
  • Ri denotes a linear or branched C1-C10 alkyl or C 2 -Cio alkenyl or C 2 -Cio alkynyl radical, optionally interrupted with one or more non-adjacent heteroatoms or groups chosen from O, N(Ra), S and C(O), and/or optionally substituted with one or more radicals, which may be identical or different, chosen from the radicals -O-R4, -S-R 4 , -NRaRb, -C(0)-0-R 4 and -C(0)-NRaRb, and the other groups R 2 , R3, R 4 , Ra and Rb have the same meanings as those set out above.
  • Ri preferably represents a linear or branched C1-C10 alkyl radical, optionally substituted with one or more radicals, which may be identical or different, chosen from the radicals -OR 4 , better still a saturated linear or branched Ci- C10, in particular Ci-C 6 , more particularly C1-C4, alkyl radical, such as a methyl or tert- butyl radical.
  • the compounds of formula (I) are chosen from the compounds (7) to (18), (21) and (22), and also the addition salts thereof, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the solvates thereof, and mixtures thereof, and better still from the compounds (7), (9) and (15).
  • Another subject of the invention is a process for preparing the compounds of formula (I) as defined previously, according to the synthesis routes A, B, C and D, described below:
  • X denoting a halogen atom such as CI, Br or I
  • Y denoting a leaving group, in particular a halogen atom, triflate or tosylate, and PG denoting an amine- function-protecting group;
  • said process comprises: - according to route A, reacting 5-aminopyrazole (a) with one molar equivalent of the compound (b) according to step i) so as to give the compound (c), which, after intramolecular reaction in the presence of a base, preferably a strong base, in particular alkali metal alkoxides such as tBu-0 " M + with M + representing an alkali metal such as K + , and in particular by heating, preferably at a temperature between 80°C and 120°C, preferably in a polar non-protic solvent such as DMSO, followed by nitration with a nitrating agent, in particular chosen from nitrites, in particular alkali metal or alkaline-earth metal nitrites such as sodium nitrite, preferably in the presence of an acid, in particular a carboxylic acid such as acetic acid, preferably in a polar protic solvent such as water, gives the nitrosopyrazole derivative (d) according to
  • step iv) which can give the compound of formula (I) according to the invention via step ii), then step iii), as defined in route A;
  • step vii) reacting the halogenated pyrazole compound (j) with one molar equivalent of the compound (k) according to step vii) so as to give the compound (m), followed by an intramolecular reaction according to step viii) so as to give the nitropyrazolo compound (n) which, after reduction, preferably catalytic reduction, in particular with Pd/C, with H 2 under pressure, according to step ix) gives the compound of formula (I) according to the invention.
  • the first step i) is a monotope reaction comprising two nucleophihc substitutions (intermolecular substitution then intramolecular substitution) so as to give the N - substituted lH-pyrazole-5 -amine compound (c).
  • the latter is deprotonated on the 5- amino group of the pyrazole by means of sodium tert-butoxide and reacts with the carbon atom in the alpha position with respect to X of the compound (c) in dimethyl sulfoxide (DMSO) under hot conditions.
  • DMSO dimethyl sulfoxide
  • the second step ii') is a nitrosation of the cyclic compound c') with sodium nitrite in an acidic medium so as to give the compound (d).
  • the by-products that are observed can form via the nitrosonium with the secondary amine or the nitrogen of pyridine type.
  • a subject of the present invention is also a cosmetic composition for dyeing keratin fibres, comprising, in a medium that is suitable for dyeing in particular keratin fibres such as the hair, one or more compounds of formula (I) as defined previously, and also the optical isomers, geometrical isomers and tautomers thereof, the addition salts thereof with an acid or a base, and the solvates thereof such as hydrates.
  • the compound(s) of formula (I), as defined previously, and also the tautomer(s), optical isomer(s) and geometrical isomer(s) thereof, the addition salts thereof with an acid or a base and the solvate(s) thereof, preferably represent from 0.001% to 10% by weight, more preferentially from 0.05%> to 6%> by weight, and even better still from 0.1 % to 3% by weight, relative to the total weight of the composition.
  • the medium that is suitable for dyeing also known as the dye support, generally comprises water or a mixture of water and of at least one organic solvent to dissolve the compounds that would not be sufficiently water-soluble.
  • the organic solvents are chosen from linear or branched and preferably saturated monoalcohols or diols, containing 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-l,5-pentanediol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycols or glycol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof such as propylene glycol monomethyl ether, butylene glycol or dipropylene glycol; and also diethylene glycol alkyl ethers, in particular of C1-C4, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
  • monoalcohols or diols containing 2
  • the common solvents described above if they are present, usually represent from 1% to 40% by weight and more preferentially from 5% to 30% by weight, relative to the total weight of the composition.
  • composition according to the present invention can optionally also comprise one or more additional oxidation base(s) different from the compound(s) of formula (I), as defined previously, which can be chosen from the oxidation bases conventionally used in oxidation dyeing.
  • the additional oxidation base(s) is (are) chosen from para- phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases different from the compound(s) of formula (I) defined previously.
  • the additional oxidation base(s) is (are) chosen from para-phenylenediamines, and more particularly chosen from para- phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl- para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, ⁇ , ⁇ -diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis( -hydroxyethyl)- para-phenylenediamine, 4-N,N-bis( -hydroxyethyl)amino-2-methylaniline, N,N
  • para-phenylenediamine para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2- ⁇ - hydroxyethyl-para-phenylenediamine, 2- -hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3- dimethyl-para-phenylenediamine, N,N-bis( -hydroxyethyl)-para-phenylenediamine, 2- chloro-para-phenylenediamine and 2- -acetylaminoethyloxy-para-phenylenediamine, and the corresponding addition salts with an acid, are particularly preferred.
  • the additional oxidation base(s) is (are) chosen from bis(phenyl)alkylenediamines, more particularly chosen from ⁇ , ⁇ '- bis( -hydroxyethyl)-N,N'-bis(4'-aminophenyl)- 1 ,3-diaminopropanol, 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- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine and
  • the additional oxidation base(s) is (are) chosen from para-aminophenols, more particularly chosen from para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2-( -hydroxyethyl-aminomethyl)phenol and 4-amino-2- fluorophenol, and the corresponding addition salts with an acid.
  • para-aminophenols more particularly chosen from para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-
  • the additional oxidation base(s) is
  • the additional oxidation base(s) is (are) chosen from heterocyclic bases, more particularly those derived from pyridine, from pyrimidine and from pyrazole that are different from the compound(s) of formula (I) defined previously.
  • pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for example 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4- diaminopyridine, and the corresponding addition salts.
  • pyridine-derived oxidation bases that are useful in the present invention are the 3-aminopyrazolo[l,5-a]pyridine oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308. Mention may, for example, be made of pyrazolo[l,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[l,5- a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[l ,5-a]pyrid-3-ylamine, 3- aminopyrazo lo [ 1 ,5 -a]pyridine-2-carboxylic acid, 2-methoxypyrazo lo [ 1 ,5 -a]pyrid-3 - ylamine, (3-aminopyrazolo[ 1 ,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[ 1 ,5- a]pyrid-5-
  • pyridine-derived additional oxidation bases that are useful in the present invention are chosen from 3-aminopyrazolo[l,5-a]pyridines and are preferably substituted on carbon atom 2 with:
  • an optionally cationic 5- to 7-membered heterocycloalkyl group comprising from 1 to 3 heteroatoms, optionally substituted with one or more (Ci-C 6 )alkyl groups such as a di(Ci-C4)alkylpiperazinium group; or
  • pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4- hydroxy-2,5 ,6-triaminopyrimidine, 2-hydroxy-4,5 ,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists.
  • a 4,5-diaminopyrazole will preferably be used and even more preferentially 4,5-diamino- l-(P-hydroxyethyl)pyrazole and/or a corresponding salt.
  • diamino-N,N-dihydropyrazolopyrazolones such as the following compounds and the corresponding addition salts: 2,3-diamino-6,7-dihydro-lH,5H-pyrazolo[l,2- ajpyrazol- 1 -one, 2-amino-3-ethylamino-6,7-dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 - one, 2-amino-3-isopropylamino-6,7-dihydro- lH,5H-pyrazolo[ 1 ,2-a]pyrazol- 1 -one, 2- amino-3-(pyrrolidin- 1 -yl)-6,7-d
  • Use will preferably be made of 2,3-diamino-6,7-dihydro-lH,5H-pyrazolo[l,2- a]pyrazol-l-one and/or a corresponding salt.
  • Heterocyclic bases that will preferably be used are 4,5-diamino- 1-( ⁇ - hydroxyethyl)pyrazole, 4,5-diamino- l-(hexyl)pyrazole and/or 2,3-diamino-6,7- dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one and/or a corresponding salt.
  • composition according to the present invention may optionally also comprise one or more coupling agents advantageously chosen from those conventionally used in the dyeing of keratin fibres.
  • the coupling agent(s) of the invention is (are) chosen from the compounds of formulae (II) and ( ⁇ ), and also the organic or mineral acid or base salts thereof, and the solvates thereof such as h drates:
  • Xi and X 2 which may be identical or different, represent a group chosen from hydroxyl, (di)(Ci-C6)(alkyl)amino or (di)hydroxy(Ci-C6)alkylamino groups;
  • - Y represents a hydrogen atom or a (Ci-C6)(hydroxy)alkyl group, or else two adjacent substituents Y and Xi and/or Y and X 2 form, together with the carbon atoms which bear them, an optionally substituted heterocyclic group, such as morpholinyl, piperazinyl, piperidinyl, preferably Y represents a hydrogen atom, a (Ci-C 6 )alkyl group, or else two adjacent substituents Y and Xi form, together with the carbon atoms which bear them, a morpholinyl group optionally substituted with a (Ci-C4)alkyl group; - p is 1, 2, 3 or 4;
  • the coupling agent(s) of the invention is (are) chosen from the compounds of formulae (II a ) and (Il'a), and also the organic or mineral acid or base salts thereof, and the solvates thereof such as h drates:
  • Xi and X 2 are as defined previously, preferably Xi and/or X 2 represent(s) a hydroxyl, amino or (hydro xy)alkylamino group;
  • - Yi represents a hydrogen atom or a (Ci -C 6 )alkyl group
  • - Y 2 represents a hydrogen atom, or forms, with the substituent Yi , an optionally substituted heterocycle, such as morpholinyl, piperazinyl or piperidinyl, preferably a morpholinyl heterocycle optionally substituted with a (Ci -C4)alkyl group.
  • an optionally substituted heterocycle such as morpholinyl, piperazinyl or piperidinyl, preferably a morpholinyl heterocycle optionally substituted with a (Ci -C4)alkyl group.
  • the coupler(s) of the invention are chosen from: 2- methylresorcinol, 6-hydroxybenzomorpholine; 2-amino-3-hydroxypyridine; 2-( ⁇ 3-[(2- hydroxyethyl)amino]-2-methylphenyl ⁇ amino)ethanol and also the acid or base salts thereof and the solvates thereof such as hydrates.
  • addition salts of oxidation bases and couplers that may be used in the context of the invention are chosen in particular from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • the composition according to the present invention may optionally also comprise one or more synthetic or natural direct dyes, chosen from cationic or non- ionic species, and preferably from cationic species.
  • Suitable direct dyes include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.
  • the direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of formulae (Ilia) and (IH'a), the azo cationic dyes (IVa) and (IV'a) and the diazo cationic dyes (Va) below:
  • Het + represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted preferably with one or more (Ci-C8)alkyl groups such as methyl;
  • Ar + represents an aryl radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, preferably ammonium, particularly tri(Ci-C8)alkyl ammonium such as trimethylammonium;
  • Ar represents an aryl group, especially phenyl, which is optionally substituted, preferably with one or more electron-donating groups such as i) optionally substituted (Ci-C8)alkyl, ii) optionally substituted (Ci-Cs)alkoxy, iii) (di)(Ci- C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(Ci-C8)alkylamino, v) optionally substituted N-(C 1 -C8)alkyl-N- aryl(Ci-C8)alkylamino or, as a variant, Ar represents a julolidine group;
  • Ar' represents an optionally substituted divalent (hetero)arylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferably with one or more groups (Ci-C8)alkyl, hydroxyl or (Ci- C8)alkoxy;
  • Ar represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferably with one or more (Ci- C8)alkyl, hydroxyl, (di)(Ci-C8)(alkyl)amino, (Ci-C8)alkoxy or phenyl groups;
  • R a and R b which may be identical or different, represent a hydrogen atom or a (Ci- C8)alkyl group, which is optionally substituted, preferably with a hydroxyl group; or, as a variant, the substituent R a with a substituent of Het + and/or R b with a substituent of Ar and/or R a with R b form, together with the atoms that bear them, a (hetero)cycloalkyl;
  • R a and R b represent a hydrogen atom or a (Ci-C4)alkyl group, which is optionally substituted with a hydroxyl group;
  • An " represents an anionic counterion, such as mesylate or halide.
  • the cationic part is derived from the following derivatives:
  • R 1 represents a (Ci-C4)alkyl group such as methyl
  • R 2 and R 3 which are identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group, such as methyl;
  • R 4 represent a hydrogen atom or an electron-donating group such as an optionally substituted (Ci-C8)alkyl group, an optionally substituted (Ci-C8)alkoxy group, or a (di)(Ci-C8)(alkyl)amino group optionally substituted on the alkyl group(s) with a hydroxyl group; in particular, R 4 represents a hydrogen atom;
  • - Z represents a CH group or a nitrogen atom, preferably CH;
  • An " represents an anionic counterion, such as mesylate or halide.
  • hennotannic acid juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts may also be used.
  • the direct dye(s), when it (they) is (are) present, preferably represent from 0.001% to 10% by weight, more preferentially from 0.005%) to 5%> by weight, relative to the total weight of the composition.
  • composition according to the invention may also optionally comprise one or more adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, non-ionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, non-ionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film- forming agents, ceramides, preservatives and opacifiers.
  • adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, non-ionic, amphoteric or
  • adjuvants are generally present in an amount, for each of them, of between 0.01% and 20% by weight relative to the total weight of the composition.
  • the pH of the dyeing composition in accordance with the invention is generally between 3 and 12 and preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents regularly used in the dyeing of keratin fibres or alternatively using conventional buffer systems.
  • acidifying agents mention may be made, for example, of mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
  • mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
  • basifying agents examples that may be mentioned include aqueous ammonia, alkali metal carbonates, alkanolamines, such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of the formula (V) below:
  • formula (V) W is a linear or branched (Ci-C6)alkylene group, in particular propylene, optionally substituted with one or more hydroxyl groups;
  • Re, R 7 , Rs and R9 which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or Ci- C 4 hydroxy alkyl radical.
  • composition according to the present invention may optionally also comprise one or more oxidizing agents.
  • the oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof, and alkali metal or alkaline-earth metal percarbonates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases such as laccases.
  • the oxidizing agent will be hydrogen peroxide, in particular as an aqueous solution (aqueous hydrogen peroxide solution), the concentration of which may range more particularly from 0.1% to 50% by weight, even more preferentially from 0.5% to 20% by weight and better still from 1% to 15% by weight relative to the weight of the aqueous solution.
  • aqueous hydrogen peroxide solution aqueous hydrogen peroxide solution
  • the oxidizing agent(s), when it (they) is (are) present, preferably represent(s) from 0.1% to 50% by weight, more preferentially from 0.5% to 20% by weight, relative to the total weight of the composition.
  • composition according to the present invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and in particular human keratin fibres such as the hair.
  • the present invention also relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, consisting in applying to said keratin fibres a cosmetic composition as defined previously, in the presence of one or more oxidizing agents.
  • the cosmetic composition used in the process according to the invention is applied to wet or dry keratin fibres.
  • the temperature during the dyeing process conventionally ranges from ambient temperature (from 15°C and 25°C) to 80°C, preferably from ambient temperature to 60° C.
  • the keratin fibres are advantageously rinsed with water. They may optionally be washed with a shampoo, followed by rinsing with water, before being dried or left to dry.
  • composition applied in the process according to the invention is generally prepared by extemporaneous mixing of at least two compositions, preferably two or three compositions.
  • the composition applied in the process according to the invention also known as the "ready-to-use" composition, is derived from the extemporaneous mixing of two compositions.
  • composition (A) (free of oxidizing agent) comprising one or more compounds of formula (I) and also the addition salts thereof, the optical isomers, geometrical isomers and tautomers thereof and/or the solvates thereof, is mixed with a composition (B) comprising one or more oxidizing agents as previously defined.
  • the term "free of” refers to a composition which does not contain any or which contains less than 0.1% by weight of oxidizing agent relative to the total weight of the composition.
  • At least one of the compositions (A) and (B) is advantageously aqueous.
  • aqueous composition is intended to mean a composition comprising at least 5% by weight of water, relative to the weight of this composition.
  • an aqueous composition comprises more than 10% by weight of water and even more advantageously more than 20% by weight of water.
  • the dyeing process according to the invention consists, in a first step, in mixing composition (A) and composition (B), as defined previously, just before application to the keratin fibres, and, in a second step, in applying to said keratin fibres the composition derived from the mixing of compositions (A) and (B).
  • a subject of the invention is also a multi-compartment device, or multi- compartment dyeing kit, comprising a first compartment containing a cosmetic composition as defined previously, and a second compartment containing an oxidizing composition comprising one or more oxidizing agents.
  • the invention also relates to a multicompartment device comprising a first compartment containing composition (A), as described above, and at least a second compartment containing composition (B), as described above; compositions (A) and (B) of the compartments being intended to be mixed before application, to give a composition according to the invention.
  • Another subject of the invention is the use of one or more compound(s) of formula (I), as defined previously, and also the tautomeric forms, optical isomers and geometrical isomers thereof, the addition salts thereof with an organic or mineral acid or base, and/or the solvates thereof, optionally in the presence of one or more additional oxidation base(s) different from the compounds of formula (I), and/or of one or more coupling agent(s), and/or of one or more oxidizing agent(s), for dyeing keratin fibres, in particular human keratin fibres such as the hair.
  • the reaction medium After cooling to approximately 0°C and with stirring, the reaction medium is slowly poured into a mixture of saturated solution of ammonium chloride and ethyl acetate. After separation of the two phases the aqueous phase is extracted three times with ethyl acetate. The combined organic phases are washed three times with water, then once with a saturated sodium bicarbonate solution and, finally, once with a saturated sodium chloride solution, before being dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product is then purified by flash chromatography on silica gel (eluent: ethyl acetate/n-heptane (20/80)). After elimination of the solvent, the expected product is isolated in the form of a white powder (2.4 g, yield of approximately 25%).
  • the aqueous phase is extracted three times with ethyl acetate and the combined organic phases are washed three times with water, then once with a saturated sodium chloride solution, before being dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • the crude product obtained is purified by flash chromatography on silica gel (eluent: ethyl acetate/n-heptane (20/80)). After elimination of the solvent, the expected product is isolated in the form of a green powder (1.55 g, yield of approximately 65%).
  • the aqueous phase is extracted three times with ethyl acetate and the combined organic phases are then washed three times with water, then once with a saturated sodium bicarbonate solution and, finally, once with a saturated sodium chloride solution, before being dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • the crude product obtained is purified by flash chromatography on silica gel (eluent: ethyl acetate/n-heptane (40/60)). After elimination of the solvent, the expected product is isolated in the form of a pale yellow powder (2.2 g, yield of approximately 18%).
  • the aqueous phase is extracted three times with ethyl acetate and the combined organic phases are washed three times with water, then once with a saturated sodium chloride solution, before being dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • the crude product obtained is purified by flash chromatography on silica gel (eluent: ethyl acetate/n-heptane (30/70-50/50)). After elimination of the solvent, the expected product is isolated in the form of an orange powder (3.0 g, yield approximately 72%).
  • 2,2-dimethylpropane (46.3 mmol) in 90 ml of DMSO (0.5 M) are introduced into a 250 ml three-necked flask equipped with a thermometer and a magnetic bar, then 13.3 g of sodium tert-butoxide (139 mmol) are added, with stirring, in small portions, before bringing the reaction medium to 120°C for 3 hours. After cooling, the reaction medium is carefully poured into a saturated solution of ammonium chloride and ethyl acetate.
  • the aqueous phase is extracted three times with ethyl acetate and the combined organic phases are washed three times in water, then with a saturated sodium bicarbonate solution and, finally, with a saturated sodium chloride solution, before being dried over anhydrous sodium sulfate and concentrated under reduced pressure.
  • the crude product obtained is purified by flash chromatography on silica gel (eluent: ethyl acetate/petroleum ether (40/60)). After elimination of the solvent, the expected product is isolated in the form of a light yellow powder (2.0 g, yield of approximately 26%).
  • the aqueous phase is extracted 3 times with ethyl acetate and the combined organic phases are washed with a saturated sodium chloride solution, before being dried over anhydrous sodium sulfate and concentrated under reduced pressure.
  • the crude product obtained is purified by flash chromatography on silica gel (eluent: ethyl acetate/petroleum ether (50/50)). After elimination of the solvent, the expected product is isolated in the form of a brown/red solid (0.8 g, yield of approximately 68%).
  • the aqueous phase is extracted 3 times with ethyl acetate and the combined organic phases are washed three times in water, then with a saturated sodium bicarbonate solution and, finally, with a saturated sodium chloride solution, before being dried over anhydrous sodium sulfate and concentrated under reduced pressure.
  • the crude product obtained is purified by flash chromatography on silica gel (eluent: ethyl acetate/petroleum ether (50/50)). After elimination of the solvent, the expected product is isolated in the form of a yellow oil (0.6 g, yield of approximately 17%).
  • the reaction medium is kept stirring at ambient temperature for 30 min, before being carefully poured into a mixture of saturated solution of sodium bicarbonate and ethyl acetate, with stirring. After separation of the two phases, the aqueous phase is extracted 3 times with ethyl acetate and the combined organic phases are washed with a saturated sodium chloride solution, before being dried over anhydrous sodium sulfate and concentrated under reduced pressure.
  • the crude product obtained is purified by flash chromatography on silica gel (eluent: ethyl acetate/petroleum ether (50/50)). After elimination of the solvent, the expected product is isolated in the form of a brown/red solid (1.35 g, yield of approximately 45%).
  • the dyeing compositions were prepared from the dyes synthesized in Examples 1 to 4 above, from the couplers as indicated in the tables below and from the dye support described hereinafter.
  • each composition is mixed with an equal weight of 20- volume aqueous hydrogen peroxide solution (6%> by weight). A final pH of 9.5 is obtained.
  • Each mixture obtained is applied to locks of grey hair containing 90% grey hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried, so as to obtain the various shades.
  • L* a* b* the three parameters denote, respectively, L* : the colour intensity, a* : the green/red colour axis, and b* : the blue/yellow colour axis.
  • L* the colour intensity
  • a* the green/red colour axis
  • b* the blue/yellow colour axis.
  • the chromaticity C* is defined according to the following equation:
  • a* and b* represent the values measured on locks of hair after colouration. The higher the C* value, the better the chromaticity of the colour.
  • the dyeing compositions A and B were prepared from the ingredients indicated in the table below:
  • composition A and B is applied to locks of natural Caucasian hair comprising 90% grey hairs, of 1 g. After a leave-on time of 30 minutes at 27°C, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The colorimetric data of each of the locks are then measured with a Minolta CM-3610d spectrophotometer.
  • the colour build-up on hair corresponds to the variation in colouring between the locks of dyed NG hair (natural grey hair containing 90% grey hairs) and the non-dyed (i.e. non-treated) NG hair, which is measured by ⁇ according to the following equation:
  • L*, a* and b* represent the values measured after dyeing of the NG hair
  • Lo*, ao* and bo* represent the values measured before dyeing of the NG hair.
  • ⁇ value the higher the ⁇ value, the better the build-up of the colouring.
  • compositions A and B are collated in the table below:
  • composition A exhibits a significantly better build-up and a significantly better chromaticity than those obtained with the comparative compound (composition B).

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Abstract

La présente invention concerne un composé de formule (I), ainsi que les formes tautomères, les isomères optiques et les isomères géométriques de celui-ci, leurs sels d'addition avec un acide ou une base, et/ou leurs solvates. L'invention concerne également l'utilisation de ces composés particuliers pour la teinture des fibres kératiniques.
PCT/EP2017/081881 2016-12-09 2017-12-07 Composé dérivé de 4,5-diaminopyrazoles comprenant un cycle fusionné, composition comprenant au moins un tel composé, procédé de mise en oeuvre et utilisation WO2018104474A1 (fr)

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FR1662220A FR3060003B1 (fr) 2016-12-09 2016-12-09 Compose derive des 4,5-diaminopyrazoles a cycle fusionne, composition comprenant au moins un tel compose, procede de mise en oeuvre et utilisation

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US11034669B2 (en) 2018-11-30 2021-06-15 Nuvation Bio Inc. Pyrrole and pyrazole compounds and methods of use thereof

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