EP1341508A1 - Dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted at least in positions 2 and 3 - Google Patents

Dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted at least in positions 2 and 3

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Publication number
EP1341508A1
EP1341508A1 EP01999348A EP01999348A EP1341508A1 EP 1341508 A1 EP1341508 A1 EP 1341508A1 EP 01999348 A EP01999348 A EP 01999348A EP 01999348 A EP01999348 A EP 01999348A EP 1341508 A1 EP1341508 A1 EP 1341508A1
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EP
European Patent Office
Prior art keywords
radical
amino
chosen
composition according
composition
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EP01999348A
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German (de)
French (fr)
Inventor
Stéphane SABELLE
Eric Terranova
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LOreal SA
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LOreal SA
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Classifications

    • 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
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • 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 subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, comprising as oxidation base a 1- (4-aminophenyl) pyrrolidine substituted for less in positions 2 and 3.
  • oxidation bases 15,6-dihydroxyindole derivatives, 5,6-dihydroxyindoline derivatives generally called oxidation bases.
  • the precursors of oxidation dyes, or oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds.
  • the dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which can be in differently sensitized effect (ie damaged) between its tip and its root. They must also have good chemical stability in the formulations. They must have a good toxicological profile.
  • NN-bis- ( ⁇ -hydroxyethyl) paraphenylenediamine and 2- ( ⁇ -hydroxyethyl) paraphenylenediamine have the disadvantage of leading to a less wide variety of shades and of imparting less color intensity, less uniformity. to hair than para-phenylenediamine and 4-amino-2-methylaniline. It is the same for 2- (hydroxyalkoxy) -paraphenylene diamine which give the hair colors which evolve and change over time.
  • the oxidation bases which are too oxidizable and which react with couplers according to accelerated reaction rates, generally lead to the formation of dyes outside the keratin fiber.
  • the intensities, tenacity and uniformity of the colorings thus obtained on the hair are generally insufficient.
  • US patent 5,851,237 proposes the use of 1- (4-aminophenyl) pyrrolidine derivatives optionally substituted on the benzene ring in order to replace paraphenylenediamine.
  • the same patent very preferably proposes the use of 1- (4-aminophenyl) pyrrolidine as a substitute for paraphenylenediamine.
  • US Patent 5,993,491 proposes the use of N- (4-aminophenyl) -2-hydroxymethylpyrrolidine derivatives optionally substituted on the benzene ring and on the pyrrolidinin heterocycle in position 4 with a hydroxy radical in order to replace paraphenylenediamine.
  • said patent proposes N- (4-aminophenyl) -2- (hydroxymethyl) -pyrrolidine substituted by a hydrogen atom or a methyl radical in position 3.
  • these compounds do not allow to give the hair a coloration of quality equivalent to that obtained with para-phenylenediamine or with paratoluenediamine due to a lack of intensity and uniformity of color.
  • Patent application JP 11158048 proposes hair coloring compositions offering good spreading properties, ease of application and resistance to shampoo. These compositions contain at least one compound chosen from 4-aminoaniline derivatives optionally substituted on the benzene ring and one of the nitrogen atoms of which is included in a 5- to 7-membered carbon ring, or, at least one compound selected from derivatives of 4-aminoaniline optionally substituted on the benzene ring and one of whose nitrogen atoms is substituted with a Z group and a radical Z 2, Z. being an alkyl, aryl or heterocycle group, and Z 2 being a radical - (CH 2 - CH 2 -O) -Z 3 where Z 3 represents a hydrogen atom, an alkyl, aryl or heterocycle group.
  • this patent application demonstrates that the preferred derivatives N- (3-isopropyloxy-4-aminophenyl) -2.5- dimethylpyrrolidine, 1- (3-methyl 4-Amino-phenyl) 2,5- dihydroxyethyl-pyrrolidine, N- (3-methyl-4-aminophenyl) -3- (2-hydroxyethyloxy) pyrrolidine, and N- (3-methyl -4-aminophenyl) -2-methyl-4-hydroxypyrrolidine behave like oxidation bases equivalent to paraphenylenediamine derivatives, the nitrogen atom of which is included in a functionalized piperidine 6-membered ring.
  • compositions containing derivatives of paraphenylenediamine having a nitrogen atom included in a functionalized pyrrolidine cycle as described in patent application JP 11158048 do not make it possible to confer on the hair dyeing results equivalent to those obtained with para -phenylenediamine or paratoluenediamine.
  • compositions for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair comprising, in a medium suitable for dyeing, - at least one base oxidation chosen from the compounds of formula (I) below, and or their addition salts with an acid
  • - Ri represents a halogen atom; a C 1 -C 7 carbon chain, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more carbon atoms of the chain being able to be replaced by an oxygen, nitrogen or sulfur atom, by an SO 2 group or by a halogen atom, the radical Ri not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals ;
  • R 3 and R 4 represent, independently of one another, a hydroxy radical; an amino radical; a saturated or unsaturated CrC 4 carbon chain; a radical -OR 6 in which R 6 represents a CC 4 alkyl radical which may be substituted by one or more radicals chosen from the group consisting of a halogen atom, a hydroxy radical, C 1 -C 2 alkoxy, amino or CC aminoalkyl 2 ; a radical -NR 7 R 8 in which R 7 and R 8 independently of one another represent a hydrogen atom, an alkyl radical in C-rC, an alkyl radical in CC 4 substituted by one or more selected radicals in the group consisting of a halogen atom, a hydroxy, CC 2 alkoxy, amino or CC 2 aminoalkyl radical, - R 2 and R 5 represent, independently of one another, a carbon chain in CC 4 , saturated or unsaturated; an alkyl radical in CC 4 substituted by an alkoxy radical in C-
  • C 4 substituted with at least one amino group and at least one hydroxy group; a carboxyl radical; a carbamoyie radical; a carbamoyl (mono or dialkyl) (CrC 4 ) radical; a
  • alkoxy (C- ⁇ -C 4 ) carbonyl radical a (C1-C4) carbonyl alkyl radical
  • R 4 and R 5 can also represent, independently of each other, a hydrogen atom
  • - n is between 0 and 2, it being understood that when n is equal to 2 then the radicals R. can be identical or different.
  • the 1- (4-aminophenyl) - pyrrolidine derivatives of formula (I) substituted at least in positions 2 and 3 of the pyrrolidine ring can be used as oxidation dye precursors, and in addition allow to obtain dye compositions which lead to powerful coloring of keratin fibers and which exhibit good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction). Finally, these compounds appear to be easily synthesizable and are chemically stable.
  • radicals, groups, or carbon chains defined above in formula (I) may be linear or branched.
  • radical Ri when it is indicated that one or more of the carbon atoms of the radical Ri may be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group, and / or that said radical Ri may contain one or more double bonds and / or one or more triple bonds, this means that the following transformations can be made, for example: -CHj— H can become '- OH
  • the radical R. is preferably chosen from a chlorine or bromine atom, a methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1 radical , 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl, 1, 2-diaminoethyl, methoxy, ethoxy, allyloxy, 2-hydroxyethyloxy.
  • R1 is chosen from a methyl, hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, methoxy, 2-hydroxyethoxy, and preferably a methyl radical.
  • n is equal to 0 or 1.
  • R is preferably in position 3 of the benzene ring.
  • the radicals R 2 and R 5 of formula (I) are preferably chosen from the hydroxymethyl radical, the aminomethyl radical, the carboxyl radical, the carbamoyie radical, the 2-hydroxyethyloxymethyl radical, the 2-hydroxyethylaminomethyl radical, and hydrogen for R 5 .
  • the radical R 2 is chosen from the hydroxymethyl, carboxyl or carbamoyie radical, and the radical R 5 from hydrogen or the hydroxymethyl radical.
  • the radicals R 3 and R of formula (I) are preferably chosen from the hydroxyl radical, the acetoxy radical, the amino radical, the methylamino radical, the dimethylamino radical, the 2-hydroxyethylamino radical, the 2-hydroxyethyloxy radical, and l 'hydrogen for R 4 .
  • R 3 preferably represents the hydroxyl radical, an amino radical and R a hydroxyl radical, an amino radical or hydrogen.
  • the asymmetric carbons substituted by the radicals R 2 and R 3 may be independently of each other of configuration (R) and / or (S).
  • R 2 and R 3 may be independently of each other of configuration (R) and / or (S).
  • the addition salts with an acid of the compounds of formula (I) according to the invention are preferably chosen from inorganic or organic salts such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates.
  • the hydrochlorides are particularly preferred.
  • the compound (s) of formula (I) according to the invention preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight .
  • the medium suitable for dyeing generally consists of water or 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 CC 4 alkanols, such as ethanol and isopropanol; polyols or 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, analogous products 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 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.
  • 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 the compounds of formula (II) below:
  • W is a propylene residue optionally substituted by a hydroxyl group or a CC 6 alkyl radical
  • R, R5, Re and R 7 which may be identical or different, represent a hydrogen atom, a CC 6 alkyl or C 1 -C 6 hydroxyalkyl radical.
  • the dye composition in accordance with the invention may also contain, in addition to the compound or compounds of formula (I) defined above, at least one additional oxidation base which can be chosen from the oxidation bases conventionally used in dyeing oxidation and among which there may be mentioned paraphenylenediamines different from the compounds of formula (I), bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols and heterocyclic bases.
  • paraphenylenediamines mention may more particularly be made, for example, of 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
  • para-phenylenediamines very particularly preferred are para-phenylenediamine, paratoluylenediamine, 2-isopropyl para-phenylenediamine, 2- ⁇ -hydroxyethyl para-phenylenediamine, 2- ⁇ -hydroxyethyloxy para-phenylenediamine, la 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- ( ⁇ -hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2- ⁇ -acetylaminoethylenediamine paraphenylenediamine , and their addition salts with an acid.
  • para-aminophenol there may be more particularly mentioned by way of example, paraaminophenol, 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.
  • paraaminophenol 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 mention may more particularly be made, by way of example, of 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 that may be mentioned more particularly by way of example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
  • pyridine derivatives mention may more particularly 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.
  • pyrazole derivatives mention may more particularly 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 such as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- ( ⁇ -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
  • these additional oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.
  • the oxidation dye compositions in accordance with the invention may also contain at least one coupler and / or at least one direct dye, in particular for modifying the nuances or enriching them with reflections.
  • the couplers which can be used in the oxidation dye compositions in accordance with the invention can be chosen from the couplers conventionally used in oxidation dyeing and among which there may be mentioned in particular metaphenylenediamines, meta-aminophenols, metadiphenols, naphthols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, pyridine derivatives, indazole derivatives, pyrazolo derivatives [1, 5-b] -1, 2,4-triazole, pyrazolo derivatives [ 3,2-c] -1, 2,4-triazole, benzimidazole derivatives, benzothiazole derivatives, benzoxazole derivatives, 1,3-benzodioxole derivatives and pyrazolones, and their addition salts with a acid.
  • metaphenylenediamines meta-aminophenols, metadiphenols, naphthols and heterocyclic couplers
  • couplers are more particularly chosen from 2-methyl 5-amino phenol, 5-N- ( ⁇ -hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1, 3-dihydroxy benzene, 1, 3 -dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino l- ( ⁇ -hydroxyethyloxy) benzene, 2-amino 4- ( ⁇ -hydroxyethylamino) 1 -methoxy benzene, 1, 3-diamino benzene, le, 3-bis- (2,4-diaminophenoxy) propane, sesamol, P ⁇ -naphthol, 2-methyl-1-naphtol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 6-hydroxy indoline, 6-hydroxybenzomorpholine, 3,5 diamino 2,6dimethoxy pyridine, 1-N ⁇ hydroxyethyl
  • the coupler or couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately of this weight.
  • the dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers , non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as by example of silicones, film-forming agents, preserving agents, opacifying agents.
  • adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers , non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing
  • 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.
  • compositions of the invention for the oxidation dyeing of keratin fibers, and in particular human fibers such as the 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.
  • At least one dye composition as defined above is applied to the fibers, the color being revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just at the time of use. the dye composition or which is applied separately, simultaneously or sequentially.
  • the dye composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient to develop coloring.
  • the mixture obtained is then applied to the keratin fibers and left to stand for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, washed with shampoo, rinsed again and dried.
  • the oxidizing agent can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bramates, persalts such as as perborates and persulfates, and the enzymes among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.
  • the pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and again more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.
  • the oxidizing composition as defined above may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
  • 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 or any other packaging system with several compartments, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition. as defined above.
  • These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, by any means known to a person skilled in the art, for example the devices described in patent FR-2,586,913 in the name of the applicant.
  • the subject of the invention is also the colored product resulting from the oxidation of at least one compound of formula (I) as defined above in the presence of at least one oxidizing agent, and optionally in the presence of at least one coupler and / or at least one additional oxidation base.
  • colored products can also be in the form of pigments and be used as direct dyes for the direct dyeing of hair or even be incorporated in cosmetic products such as for example in makeup products.
  • cosmetic products such as for example in makeup products.
  • the examples which follow are intended to illustrate the invention without however limiting its scope.
  • the reactor is then purged with nitrogen and the reaction medium is filtered under a nitrogen atmosphere and the filtrate is immediately recovered in a solution containing 20 ml of 37% hydrochloric acid and 180 ml of isopropanol.
  • the filtrate is then concentrated until a precipitate is obtained.
  • the solid is filtered, washed with isopropanol then with ethyl ether and dried under vacuum in the presence of potassium hydroxide. 15.65 g (83%) of 1- (4-Amino-phenyl) -2-hydroxymethyl-pyrrolidin-3-ol dihydrochloride (4) are thus obtained in the form of a white solid.
  • each dye composition is mixed with an equal amount of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight) and having a pH of approximately 3.
  • Each mixture obtained has a pH of approximately 9.5 and is applied for 30 minutes to locks of natural gray hair containing 90% white hairs. The locks of hair are then rinsed, washed with a standard shampoo and then dried.

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Abstract

The invention concerns a composition for oxidation dyeing of keratinous fibres, and in particular human keratinous fibres such as hair, comprising as oxidation base a 1-(4-aminophenyl) pyrrolidine substituted at least in positions 2 and 3. The invention also concerns the method for oxidation dyeing of keratinous fibres using said compositions.

Description

COMPOSITION DE TEINTURE A BASE DE 1- (4-AMINOPHENYL) PYRROLIDINES SUBSTITUEES AU MOINS EN POSITION 2 ET 3DYE COMPOSITION BASED ON 1- (4-AMINOPHENYL) PYRROLIDINES SUBSTITUTED AT LEAST 2 AND 3
5 L'invention a pour objet une composition pour la teinture d'oxydation des fibres kératiniques, et en particulier des fibres kératiniques humaines telles que les cheveux, comprenant à titre de base d'oxydation une 1-(4-aminophényl)pyrrolidine substituée au moins en positions 2 et 3.5 The subject of the invention is a composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair, comprising as oxidation base a 1- (4-aminophenyl) pyrrolidine substituted for less in positions 2 and 3.
10 II est connu de teindre les fibres kératiniques et en particulier les cheveux humains avec des compositions tinctoriales contenant des précurseurs de colorant d'oxydation, en particulier des ortho ou para-phénylènediamines, des ortho ou para-aminophénols, des composés hétérocycliques tels que des dérivés de diaminopyrazole, des dérivés de pyrazolo[1 ,5-a]pyrimidine, des dérivés de pyrimidines, des dérivés de pyridine, desIt is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, heterocyclic compounds such as diaminopyrazole derivatives, pyrazolo [1,5-a] pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives,
15 dérivés de 5,6-dihydroxyindole, des dérivés de 5,6-dihydroxyindoline appelés généralement bases d'oxydation. Les précurseurs de colorants d'oxydation, ou bases d'oxydation, sont des composés incolores ou faiblement colorés qui, associés à des produits oxydants, peuvent donner naissance par un processus de condensation oxydative à des composés colorés et colorants.15,6-dihydroxyindole derivatives, 5,6-dihydroxyindoline derivatives generally called oxidation bases. The precursors of oxidation dyes, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds.
2020
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 méta-diamines aromatiques, les méta-aminophénols, les méta-hydroxyphénols et certains composés hétérocycliques tels que par exemple desIt is also known that the shades obtained with these oxidation bases can be varied by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta- hydroxyphenols and certain heterocyclic compounds such as for example
25 dérivés de pyrazolo[1 ,5-b]-1 ,2,4,-triazoles, des dérivés de pyrazolo[3,2-c]-1 ,2,4,-triazoles,. des dérivés de pyrazolo[1,5-a]pyrimidines , des dérivés de pyridine, des dérivés de pyrazol-5-one, des dérivés d'indoline et des dérivés d'indole.Derivatives of pyrazolo [1, 5-b] -1, 2,4, -triazoles, derivatives of pyrazolo [3,2-c] -1, 2,4, -triazoles ,. pyrazolo [1,5-a] pyrimidines derivatives, pyridine derivatives, pyrazol-5-one derivatives, indoline derivatives and indole derivatives.
La variété des molécules mises en jeu au niveau des bases d'oxydation et des coupleurs, 30 permet l'obtention d'une riche palette de couleurs.The variety of molecules involved in the oxidation bases and couplers, allows a rich palette of colors to be obtained.
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 inconvénient sur le plan toxicologique, elle doit permettre d'obtenir des nuances dans l'intensitéThe so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain nuances in the intensity
35 souhaitée, présenter une bonne tenue face aux agents extérieurs (lumière, intempéries, lavage, ondulation permanente, transpiration, frottements). Les colorants doivent également permettre de couvrir les cheveux blancs, et être enfin les moins sélectifs possible, c'est à dire permettre d'obtenir des écarts de coloration les plus faibles possible tout au long d'une même fibre kératinique, qui peut être en effet différemment sensibilisée (i.e. abîmée) entre sa pointe et sa racine. Ils doivent également présenter une bonne stabilité chimique dans les formulations. Ils doivent présenter un bon profil toxicologique.35 desired, have good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction). The dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which can be in differently sensitized effect (ie damaged) between its tip and its root. They must also have good chemical stability in the formulations. They must have a good toxicological profile.
Dans le domaine de la coloration capillaire, la para-phénylènediamine, la paratoluène diamine sont des bases d'oxydation largement utilisées. Elles permettent d'obtenir avec des coupleurs d'oxydation des nuances variées.In the field of hair coloring, para-phenylenediamine and paratoluene diamine are widely used oxidation bases. They make it possible to obtain various nuances with oxidation couplers.
Cependant, Il existe un besoin de découvrir de nouvelles base d'oxydation présentant un meilleur profil toxicologique que la para-phénylènediamine et la paratoluène diamine, tout en permettant de conférer aux cheveux d'excellente propriétés d'intensité de couleur, de variété de nuances, d'uniformité de la couleur et de ténacité aux agents extérieursHowever, there is a need to discover new oxidation bases having a better toxicological profile than para-phenylenediamine and paratoluene diamine, while making it possible to give the hair excellent properties of color intensity, variety of shades. , color uniformity and tenacity to external agents
Il a déjà été proposé, notamment dans la demande de brevet GB 2 239 265, d'utiliser de la 2-(β-hydroxyéthyl) paraphénylènediamine ou bien encore de la N,N-bis-(β- hydroxyéthyl) paraphénylènediamine comme des remplaçants potentiels de la paraphénylènediamine et de paratoluylènediamine. Il en est de même pour les 2- (hydroxyalcoxy) paraphénylènediamines (voir notamment le brevet US 5 538 516).It has already been proposed, in particular in patent application GB 2 239 265, to use 2- (β-hydroxyethyl) para-phenylenediamine or else N, N-bis- (β-hydroxyethyl) para-phenylenediamine as substitutes potentials of paraphenylenediamine and paratoluylenediamine. The same is true for 2- (hydroxyalkoxy) paraphenylenediamines (see in particular US Pat. No. 5,538,516).
Cependant, la N.N-bis-(β-hydroxyéthyl) paraphénylènediamine et le 2-(β-hydroxyéthyl) paraphénylènediamine présentent l'inconvénient de conduire à une variété de nuances moins large et de conférer moins d'intensité de couleur, moins d'uniformité aux cheveux que la para-phénylènediamine et le 4-amino-2-méthylaniline. Il en est de même pour les 2-(hydroxyalcoxy)-paraphénylène diamine qui confèrent aux cheveux des couleurs qui évoluent et changent au cours du temps.However, NN-bis- (β-hydroxyethyl) paraphenylenediamine and 2- (β-hydroxyethyl) paraphenylenediamine have the disadvantage of leading to a less wide variety of shades and of imparting less color intensity, less uniformity. to hair than para-phenylenediamine and 4-amino-2-methylaniline. It is the same for 2- (hydroxyalkoxy) -paraphenylene diamine which give the hair colors which evolve and change over time.
Par ailleurs, Il est connu dans la littérature (R.L. Bent et coll. , J.A.C.S. 73, 3100, 1951) que les dérivés de 4-paraphénylènediamine dont un des atomes d'azote est compris dans un cycle non aromatique à 6 ou 7 chaînons carbonés ou hétérocycliques sont moins oxydables que les dérivés de 4- paraphénylènediamines dont un des atomes d'azote est substitué par deux substituants dissymétriques, qui sont eux mêmes moins oxydables que les dérivés de paraphénylènediamine dont un des atomes d'azote est substitué par deux substituants symétriques. Il est également mentionné dans le même article que le dérivé de paraphénylènediamine dont un des atomes d'azote est compris dans un cycle non aromatique à 5 chaînons carbonés est plus oxydable que chacun des dérivés cités ci dessus. Cette classe particulière de dérivés de N-(4-aminophényl)-pyrrolidine permet donc d'obtenir des réactions de condensation avec des coupleurs en milieu oxydant dont la cinétique se trouve être accélérée par rapport aux dérivés de paraphénylènediamine cités ci-dessus.Furthermore, it is known in the literature (RL Bent et al., JACS 73, 3100, 1951) that 4-paraphenylenediamine derivatives in which one of the nitrogen atoms is included in a non-aromatic 6 or 7-membered carbon ring or heterocyclic compounds are less oxidizable than the derivatives of 4-paraphenylenediamines in which one of the nitrogen atoms is substituted by two asymmetric substituents, which are themselves less oxidizable than the derivatives in paraphenylenediamine in which one of the nitrogen atoms is substituted by two symmetrical substituents . It is also mentioned in the same article that the paraphenylenediamine derivative, one of the nitrogen atoms of which is included in a nonaromatic 5-carbon chain ring is more oxidizable than each of the derivatives mentioned above. This particular class of N- (4-aminophenyl) -pyrrolidine derivatives therefore makes it possible to obtain condensation reactions with couplers in an oxidizing medium whose kinetics is found to be accelerated compared to the para-phenylenediamine derivatives mentioned above.
Cependant, les bases d'oxydation qui sont trop oxydables et qui réagissent avec des coupleurs selon des vitesses de réaction accélérées, conduisent généralement à la formation des colorants à l'extérieur de la fibre kératinique. Les intensités, les ténacités et l'uniformité des colorations ainsi obtenues sur les cheveux sont généralement insuffisantes.However, the oxidation bases which are too oxidizable and which react with couplers according to accelerated reaction rates, generally lead to the formation of dyes outside the keratin fiber. The intensities, tenacity and uniformity of the colorings thus obtained on the hair are generally insufficient.
Toutefois, le brevet US 5,851,237 propose l'utilisation de dérivés 1-(4-aminophényl)pyrrolidine éventuellement substitués sur le noyau benzénique afin de remplacer la paraphénylènediamine. A ce titre, le même brevet propose très préférentiellement l'utilisation de la 1-(4-aminophényl)pyrrolidine comme substitut de la paraphénylènediamine.However, US patent 5,851,237 proposes the use of 1- (4-aminophenyl) pyrrolidine derivatives optionally substituted on the benzene ring in order to replace paraphenylenediamine. As such, the same patent very preferably proposes the use of 1- (4-aminophenyl) pyrrolidine as a substitute for paraphenylenediamine.
Or, il est connu dans la littérature que le 1-(4-aminophényl)pyrrolidine possède une activité fortement allergène (R.L. Bent et coll. , J.A.C.S. 73, 3100, 1951 ).However, it is known in the literature that 1- (4-aminophenyl) pyrrolidine has a highly allergenic activity (R.L. Bent et al., J.A.C.S. 73, 3100, 1951).
Le brevet US 5,993,491 propose l'utilisation de dérivés de N-(4-aminophényl)-2- hydroxyméthylpyrrolidine éventuellement substitués sur le noyau benzénique et sur l'hétérocycle pyrrolidinique en position 4 par un radical hydroxy afin de remplacer la paraphénylènediamine. Comme composés préférés, ledit brevet propose le N-(4- aminophényl)-2-(hydroxyméthyl)-pyrrolidine substitué par un atome d'hydrogène ou un radical méthyle en position 3. Cependant, il est clairement établi que ces composés ne permettent pas de conférer aux cheveux une coloration de qualité équivalente à celle obtenue avec la para-phénylènediamine ou avec la paratoluènediamine du fait d'un manque d'intensité et d'uniformité de la couleur.US Patent 5,993,491 proposes the use of N- (4-aminophenyl) -2-hydroxymethylpyrrolidine derivatives optionally substituted on the benzene ring and on the pyrrolidinin heterocycle in position 4 with a hydroxy radical in order to replace paraphenylenediamine. As preferred compounds, said patent proposes N- (4-aminophenyl) -2- (hydroxymethyl) -pyrrolidine substituted by a hydrogen atom or a methyl radical in position 3. However, it is clearly established that these compounds do not allow to give the hair a coloration of quality equivalent to that obtained with para-phenylenediamine or with paratoluenediamine due to a lack of intensity and uniformity of color.
La demande de brevet JP 11158048 propose des compositions de coloration capillaires offrant de bonnes propriétés d'étalement, de facilité d'application et de tenue au shampoing. Ces compositions contiennent au moins un composé choisi parmi des dérivés de 4-aminoaniline éventuellement substitués sur le noyau benzénique et dont un des atomes d'azote est compris dans un cycle de 5 à 7 chaînons carbonés, ou, au moins un composé choisi parmi des dérivés de 4-aminoaniline éventuellement substitués sur le noyau benzénique et dont un des atomes d'azote est substitué par un radical Z. et un radical Z2, Z. étant un groupe alkyle, aryle ou hétérocycle, et Z2 étant un radical -(CH2- CH2-O)-Z3 où Z3 représente un atome d'hydrogène, un groupe alkyle, aryle ou hétérocycle.Patent application JP 11158048 proposes hair coloring compositions offering good spreading properties, ease of application and resistance to shampoo. These compositions contain at least one compound chosen from 4-aminoaniline derivatives optionally substituted on the benzene ring and one of the nitrogen atoms of which is included in a 5- to 7-membered carbon ring, or, at least one compound selected from derivatives of 4-aminoaniline optionally substituted on the benzene ring and one of whose nitrogen atoms is substituted with a Z group and a radical Z 2, Z. being an alkyl, aryl or heterocycle group, and Z 2 being a radical - (CH 2 - CH 2 -O) -Z 3 where Z 3 represents a hydrogen atom, an alkyl, aryl or heterocycle group.
En terme de pouvoir colorant, de facilité d'application, d'uniformité de teinte et de tenue au shampoing, cette demande de brevet met en évidence que les dérivés préférés N-(3- isopropyloxy-4-aminophényl)-2,5-diméthylpyrrolidine , 1-(3-méthyl 4-Amino-phényl) 2,5- dihydroxyéthyl-pyrrolidine , N-(3-méthyl-4-aminophényl)-3-(2-hydroxyéthyloxy)pyrrolidine, et N-(3-méthyl-4-aminophényl)-2-méthyl-4-hydroxypyrrolidine se comportent comme des bases d'oxydation équivalentes aux dérivés de paraphénylènediamine dont l'atome d'azote est compris dans un cycle à 6 chaînons pipéridinique fonctionnalisé.In terms of coloring power, ease of application, uniformity of color and resistance to shampooing, this patent application demonstrates that the preferred derivatives N- (3-isopropyloxy-4-aminophenyl) -2.5- dimethylpyrrolidine, 1- (3-methyl 4-Amino-phenyl) 2,5- dihydroxyethyl-pyrrolidine, N- (3-methyl-4-aminophenyl) -3- (2-hydroxyethyloxy) pyrrolidine, and N- (3-methyl -4-aminophenyl) -2-methyl-4-hydroxypyrrolidine behave like oxidation bases equivalent to paraphenylenediamine derivatives, the nitrogen atom of which is included in a functionalized piperidine 6-membered ring.
Or, il , est connu que lorsque l'un des atomes d'azote des dérivés de paraphénylènediamine est compris dans un cycle à 6 chaînons, notamment pipéridinique, l'énergie d'activation pour conduire à la forme oxydée quinonimine correspondante est parmi les plus élevée de la série des paraphénylènediamine N,N- disubstituées. Par conséquent, les réactions de condensation oxydative de telles bases avec ou sans coupleurs sont cinétiquement et énergetiquement défavorisées et les compositions tinctoriales contenant de telles bases d'oxydation confèrent aux cheveux des propriétés insuffisantes au niveau de l'intensité et de l'uniformité de la couleur comparativement à celles contenant de la para-phénylènediamine ou de la paratoluènediamine.However, it is known that when one of the nitrogen atoms of the paraphenylenediamine derivatives is included in a 6-membered ring, in particular piperidine, the activation energy to lead to the corresponding oxidized quinonimine form is among the most high from the series of para-phenylenediamine N, N-disubstituted. Consequently, the oxidative condensation reactions of such bases with or without couplers are kinetically and energetically disadvantaged and the dye compositions containing such oxidation bases give the hair insufficient properties in terms of intensity and uniformity of the color. color compared to those containing para-phenylenediamine or paratoluenediamine.
Il en résulte que les compositions contenant des dérivés de paraphénylènediamine ayant un atome d'azote compris dans un cycle pyrrolidinique fonctionalisé tels que décrit dans la demande de brevet JP 11158048 ne permettent pas de conférer aux cheveux des résultats tinctoriaux équivalents à ceux obtenus avec la para-phénylènediamine ou la paratoluènediamine.It follows that the compositions containing derivatives of paraphenylenediamine having a nitrogen atom included in a functionalized pyrrolidine cycle as described in patent application JP 11158048 do not make it possible to confer on the hair dyeing results equivalent to those obtained with para -phenylenediamine or paratoluenediamine.
Il est donc clair qu'il existe un réel besoin de découvrir de nouvelles bases d'oxydation présentant à la fois un bon profil toxicologique et des propriétés telles que les compositions les contenant permettent de conférer aux cheveux d'excellentes propriétés d'intensité de couleur, de variété de nuances, d'uniformité de la couleur et de ténacité vis à vis des différentes agressions extérieures que peuvent subir les cheveux. Le but de la présente invention est de développer de nouvelles compositions tinctoriales ne présentant pas les inconvénients des bases d'oxydation de la technique antérieure.It is therefore clear that there is a real need to discover new oxidation bases having both a good toxicological profile and properties such as the compositions containing them make it possible to confer excellent properties of color intensity on the hair. , variety of shades, uniformity of color and tenacity with regard to the different external aggressions that the hair can undergo. The aim of the present invention is to develop new dye compositions which do not have the drawbacks of the oxidation bases of the prior art.
Ce but est atteint avec la présente invention qui a pour objet une composition pour la teinture d'oxydation des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, comprenant, dans un milieu approprié pour la teinture, - au moins une base d'oxydation choisie parmi les composés de formule (I) suivante, et ou leurs sels d'addition avec un acideThis object is achieved with the present invention which relates to a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, - at least one base oxidation chosen from the compounds of formula (I) below, and or their addition salts with an acid
dans laquelle : in which :
- Ri représente un atome d'halogène ; une chaîne carbonée en C1-C7, saturée ou pouvant contenir une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples, linéaire ou ramifiée pouvant être sous forme de cycle ayant de 3 à 6 chaînons, un ou plusieurs atomes de carbone de la chaîne pouvant être remplacés par un atome d'oxygène, d'azote ou de soufre, par un groupe SO2 ou par un atome d'halogène, le radical R-i ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;- Ri represents a halogen atom; a C 1 -C 7 carbon chain, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more carbon atoms of the chain being able to be replaced by an oxygen, nitrogen or sulfur atom, by an SO 2 group or by a halogen atom, the radical Ri not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals ;
- R3 et R4 représentent, indépendamment l'un de l'autre un radical hydroxy ; un radical amino ; une chaîne carbonée en CrC4 saturée ou insaturée ; un radical -OR6 dans lequel R6 représente un radical alkyle en C C4 pouvant être substitué par un ou plusieurs radicaux choisis dans le groupe constitué par un atome d'halogène, un radical hydroxy, alcoxy en CrC2, amino ou aminoalkyle en C C2 ; un radical -NR7R8 dans lequel R7 et R8 représentent indépendamment l'un de l'autre un atome d'hydrogène, un radical alkyle en C-rC , un radical alkyle en C C4 substitué par un ou plusieurs radicaux choisis dans le groupe constitué par un atome d'halogène, un radical hydroxy, alcoxy en C C2, amino ou aminoalkyle en C C2, - R2 et R5 représentent, indépendamment l'un de l'autre, une chaîne carbonée en C C4, saturée ou insaturée ; un radical alkyle en C C4 substitué par un radical alcoxy en C-|-C4, acétoxy, amino, carboxyle, carbamoyie, (mono ou dialkyl)(Cι-C )carbamoyle, alkoxy(C C4)carbonyle, monohydroxyalcoxy en Çι-C6 ou par un groupe polyhydroxyalcoxy en C2-C6 ; un radical monohydroxyalkyle en CrC ; un radical polyhydroxyalkyle en Cι-C6 ; un radical aminoalkyle en Cι-C dont l'aminé est mono ou disubstituée par un radical alkyle en C-ι-C4, acétyle, monohydroxyalkyle en CrC ou polyhydroxyalkyle en C2-C6 ; un radical polyaminoalkyle en C2-C ; un radical alkyle en C2-- R 3 and R 4 represent, independently of one another, a hydroxy radical; an amino radical; a saturated or unsaturated CrC 4 carbon chain; a radical -OR 6 in which R 6 represents a CC 4 alkyl radical which may be substituted by one or more radicals chosen from the group consisting of a halogen atom, a hydroxy radical, C 1 -C 2 alkoxy, amino or CC aminoalkyl 2 ; a radical -NR 7 R 8 in which R 7 and R 8 independently of one another represent a hydrogen atom, an alkyl radical in C-rC, an alkyl radical in CC 4 substituted by one or more selected radicals in the group consisting of a halogen atom, a hydroxy, CC 2 alkoxy, amino or CC 2 aminoalkyl radical, - R 2 and R 5 represent, independently of one another, a carbon chain in CC 4 , saturated or unsaturated; an alkyl radical in CC 4 substituted by an alkoxy radical in C- | -C 4 , acetoxy, amino, carboxyl, carbamoyie, (mono or dialkyl) (Cι-C) carbamoyl, alkoxy (CC 4 ) carbonyl, monohydroxyalkoxy in Çι- C 6 or by a C 2 -C 6 polyhydroxyalkoxy group; a C r C monohydroxyalkyl radical; a Cι-C 6 polyhydroxyalkyl radical; a Cι-C aminoalkyl radical in which the amine is mono or disubstituted by a C-ι-C 4 alkyl, acetyl, C -C monohydroxyalkyl or C 2 -C 6 polyhydroxyalkyl radical; a C 2 -C polyaminoalkyl radical; a C 2 alkyl radical -
C4 substitué par au moins un groupe amino et au moins un groupe hydroxy ; un radical carboxyle ; un radical carbamoyie ; un radical (mono ou dialkyl)(CrC4)carbamoyle ; unC 4 substituted with at least one amino group and at least one hydroxy group; a carboxyl radical; a carbamoyie radical; a carbamoyl (mono or dialkyl) (CrC 4 ) radical; a
, radical alkoxy(C-ι-C4)carbonyle ; un radical alkyl (C1-C4)carbonyle, alkoxy (C-ι-C 4 ) carbonyl radical; a (C1-C4) carbonyl alkyl radical
- R4 et R5 peuvent aussi représenter indépendamment l'un de l'autre un atome d'hydrogène- R 4 and R 5 can also represent, independently of each other, a hydrogen atom
- n est compris entre 0 et 2, étant entendu que lorsque n est égal à 2 alors les radicaux R. peuvent être identiques ou différents.- n is between 0 and 2, it being understood that when n is equal to 2 then the radicals R. can be identical or different.
De façon totalement inattendue et surprenante, les dérivés de 1-(4-aminophényl)- pyrrolidine de formule (I) substitués au moins en position 2 et 3 du cycle pyrrolidinique peuvent être utilisés comme précurseurs de colorant d'oxydation, et en outre permettent d'obtenir des compositions tinctoriales qui conduisent à des colorations puissantes de fibres kératiniques et qui présentent une bonne tenue face aux agents extérieurs (lumière, intempéries, lavage, ondulation permanente, transpiration, frottements). Enfin, ces composés s'avèrent être aisément synthétisables et sont chimiquement stables.Totally unexpectedly and surprisingly, the 1- (4-aminophenyl) - pyrrolidine derivatives of formula (I) substituted at least in positions 2 and 3 of the pyrrolidine ring can be used as oxidation dye precursors, and in addition allow to obtain dye compositions which lead to powerful coloring of keratin fibers and which exhibit good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction). Finally, these compounds appear to be easily synthesizable and are chemically stable.
Sauf indication contraire, les radicaux, groupements, ou chaînes carbonées, définis précédemment dans la formule (I) peuvent être linéaires ou ramifiés.Unless otherwise indicated, the radicals, groups, or carbon chains defined above in formula (I) may be linear or branched.
Selon l'invention, lorsque qu'il est indiqué que un ou plusieurs des atomes de carbone du radical Ri peuvent être remplacés par un atome d'oxygène, d'azote, ou de soufre ou par un groupement SO2, et/ou que ledit radical R-i peut contenir une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples, cela signifie que l'on peut, à titre d'exemple, faire les transformations suivantes : -CHj— H peut devenir ' — O-HAccording to the invention, when it is indicated that one or more of the carbon atoms of the radical Ri may be replaced by an oxygen, nitrogen or sulfur atom or by an SO 2 group, and / or that said radical Ri may contain one or more double bonds and / or one or more triple bonds, this means that the following transformations can be made, for example: -CHj— H can become '- OH
Dans la formule (I), le radical R. est de préférence choisi parmi un atome de chlore ou de brome, un radical méthyle, éthyle, isopropyle, vinyle, allyle, méthoxyméthyle, hydroxyméthyle, 1-carboxyméthyle, 1-aminométhyle, 2-carboxyéthyle, 2-hydroxyéthyle, 3- hydroxypropyle, 1 ,2-dihydroxyéthyle, 1-hydroxy-2-aminoéthyle, 1-amino-2-hydroxyéthyle, 1 ,2-diaminoéthyle, méthoxy, éthoxy, allyloxy, 2-hydroxyéthyloxy. Selon un mode de réalisation particulier, R1 est choisi parmi un radical méthyle, hydroxyméthyle, 2- hydroxy éthyle, 1 ,2-dihydroxyéthyle, méthoxy, 2-hydroxyéthoxy, et préférentiellement un radical méthyle.In formula (I), the radical R. is preferably chosen from a chlorine or bromine atom, a methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1 radical , 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl, 1, 2-diaminoethyl, methoxy, ethoxy, allyloxy, 2-hydroxyethyloxy. According to a particular embodiment, R1 is chosen from a methyl, hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, methoxy, 2-hydroxyethoxy, and preferably a methyl radical.
Selon un mode de réalisation particulier, n est égal à 0 ou 1. Lorsque n est égal à 1 , alors R est de préférence en position 3 du cycle benzénique.According to a particular embodiment, n is equal to 0 or 1. When n is equal to 1, then R is preferably in position 3 of the benzene ring.
Les radicaux R2 et R5 de la formule (I) sont de préférence choisis parmi le radical hydroxyméthyle, le radical aminométhyle, le radical carboxyle, le radical carbamoyie, le radical 2-hydroxyéthyloxyméthyle, le radical 2-hydroxyéthylaminométhyle, et l'hydrogène pour R5. Selon un mode de réalisation particulier, le radical R2 est choisi parmi le radical hydroxyméthyle, carboxyle ou carbamoyie, et le radical R5 parmi l'hydrogène ou le radical hydroxymethyl.The radicals R 2 and R 5 of formula (I) are preferably chosen from the hydroxymethyl radical, the aminomethyl radical, the carboxyl radical, the carbamoyie radical, the 2-hydroxyethyloxymethyl radical, the 2-hydroxyethylaminomethyl radical, and hydrogen for R 5 . According to a particular embodiment, the radical R 2 is chosen from the hydroxymethyl, carboxyl or carbamoyie radical, and the radical R 5 from hydrogen or the hydroxymethyl radical.
Les radicaux R3 et R de formule (I) sont de préférence choisi parmi le radical hydroxyle, le radical acétoxy, le radical amino, le radical méthylamino, le radical diméthylamino, le radical 2-hydroxyéthylamino, le radical 2-hydroxyéthyloxy, et l'hydrogène pour R4. Parmi ces substituants, R3 représente de préférence le radical hydroxyle, un radical amino et R un radical hydroxyle, un radical amino ou l'hydrogène.The radicals R 3 and R of formula (I) are preferably chosen from the hydroxyl radical, the acetoxy radical, the amino radical, the methylamino radical, the dimethylamino radical, the 2-hydroxyethylamino radical, the 2-hydroxyethyloxy radical, and l 'hydrogen for R 4 . Among these substituents, R 3 preferably represents the hydroxyl radical, an amino radical and R a hydroxyl radical, an amino radical or hydrogen.
Dans la formule (I), les carbones asymétriques substitués par les radicaux R2 et R3 peuvent être indépendamment l'un de l'autre de configuration (R) et/ou (S). Parmi les composés de formule (I) utiles pour la présente invention, on peut citer en particulier :In formula (I), the asymmetric carbons substituted by the radicals R 2 and R 3 may be independently of each other of configuration (R) and / or (S). Among the compounds of formula (I) useful for the present invention, there may be mentioned in particular:
et leurs sels d'addition avec un acide.and their addition salts with an acid.
Les sels d'addition avec un acide des composés de formule (I) conforme à l'invention, sont de préférence choisis parmi les sels inorganiques ou organiques tels que les chlorhydrates, les bromhydrates, les sulfates, les citrates, les succinates, les tartrates, les lactates et les acétates. Les chlorhydrates sont particulièrement préférés.The addition salts with an acid of the compounds of formula (I) according to the invention are preferably chosen from inorganic or organic salts such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates. The hydrochlorides are particularly preferred.
Les dérivés de paraphénylènediamine à groupement pyrrolidinyle de formule (I), ainsi que leurs procédés de synthèse sont connus, voir notamment la demande de brevet DE 4 241 532 (AGFA).Paraphenylenediamine derivatives with pyrrolidinyl group of formula (I), as well as their methods of synthesis are known, see in particular patent application DE 4 241 532 (AGFA).
Le ou les composés de formule (I) conformes à l'invention représentent de préférence de 0,0005 à 12 % en poids environ du poids total de la composition tinctoriale, et encore plus préférentiellement de 0,005 à 6 % en poids environ de ce poids.The compound (s) of formula (I) according to the invention preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight .
Le milieu approprié pour la teinture (ou support) 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 C C4, tels que l'éthanol et l'isopropanol ; les polyols ou 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, les produits analogues et leurs mélanges.The medium suitable for dyeing (or support) generally consists of water or 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 CC 4 alkanols, such as ethanol and isopropanol; polyols or 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, analogous products 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 préférentiellement 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.
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.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.
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 (II) 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 the compounds of formula (II) below:
dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C C6 ; R , R5, Re et R7, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C C6 ou hydroxyalkyle en CrC6. in which W is a propylene residue optionally substituted by a hydroxyl group or a CC 6 alkyl radical; R, R5, Re and R 7 , which may be identical or different, represent a hydrogen atom, a CC 6 alkyl or C 1 -C 6 hydroxyalkyl radical.
La composition tinctoriale conforme à l'invention peut encore contenir, en plus du ou des composés de formule (I) définis ci-dessus, au moins une base d'oxydation additionnelle qui peut être choisie parmi les bases d'oxydation classiquement utilisées en teinture d'oxydation et parmi lesquelles on peut notamment citer les paraphénylènediamines différentes des composés de formule (I), les bis-phénylalkylènediamines, les paraaminophénols, les ortho-aminophénols et les bases hétérocycliques.The dye composition in accordance with the invention may also contain, in addition to the compound or compounds of formula (I) defined above, at least one additional oxidation base which can be chosen from the oxidation bases conventionally used in dyeing oxidation and among which there may be mentioned paraphenylenediamines different from the compounds of formula (I), bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols and heterocyclic bases.
Parmi les paraphénylènediamines, on peut plus particulièrement 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, la 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.Among the paraphenylenediamines, mention may more particularly be made, for example, of 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-hydroxymethyl paraphenylenediamine, N, N-dimethyl 3-methyl paraphenylen , N- (ethyl, β- hydroxyethyl) paraphenylenediamine, the N- (β, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2-β-acetylaminoethyloxy paraphenylenedaphenylenediamine methoxyethyl) paraphenylenediamine, and their addition salts with an acid.
Parmi les paraphénylènediamines citées ci-dessus, on préfère tout particulièrement 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-acétylaminoéthyIoxy paraphénylènediamine, et leurs sels d'addition avec un acide.Among the para-phenylenediamines mentioned above, very particularly preferred are para-phenylenediamine, paratoluylenediamine, 2-isopropyl para-phenylenediamine, 2-β-hydroxyethyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, la 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro paraphenylenediamine, 2-β-acetylaminoethylenediamine paraphenylenediamine , and their addition salts with an acid.
Parmi les bis-phénylalkylènediamines, on peut plus particulièrement 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)-3,5-dioxaoctane, et leurs sels d'addition avec un acide.Mention may more particularly be made, among bis-phenylalkylenediamines, by way of example, of 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) -3,5-dioxaoctane, and their addition salts with an acid.
Parmi les para-aminophénols, on peut plus particulièrement citer à titre d'exemple, le paraaminophénol, 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 more particularly mentioned by way of example, paraaminophenol, 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 plus particulièrement 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, mention may more particularly be made, by way of example, of 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 plus particulièrement citer à titre d'exemple, les dérivés pyridiniques, les dérivés pyrimidiniques et les dérivés pyrazoliques.Among the heterocyclic bases that may be mentioned more particularly by way of example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Parmi les dérivés pyridiniques, on peut plus particulièrement 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 more particularly 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 plus particulièrement citer les composés décrits par exemple dans les brevets DE 2 359 399 ; JP 88-169 571 ; JP 05 163 124 ; EP 0 770Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in patents 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 de 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 pyrazolo-[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)-amino]-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.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 mention may be made of pyrazolo- [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo- [1,5-a] - pyrimidine-3,7-diamine; pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 3-amino pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) - ethanol, 2- (7-amino pyrazolo- [1,5-a] -pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1, 5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -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, 2,5,5 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 acid addition salts and their tautomeric forms, when there is a tautomeric equilibrium .
Parmi les dérivés pyrazoliques, on peut plus particulièrement 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 more particularly 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 such 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-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1, 3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino 4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with a acid.
Lorsqu'elles sont utilisées, ces bases d'oxydation additionnelles représentent de préférence de 0,0005 à 12 % en poids environ du poids total de la composition tinctoriale, et encore plus préférentiellement de 0,005 à 6 % en poids environ de ce poids. Les compositions de teinture d'oxydation conformes à l'invention peuvent également renfermer au moins un coupleur et/ou au moins un colorant direct, notamment pour modifier les nuances ou les enrichir en reflets.When used, these additional oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight. The oxidation dye compositions in accordance with the invention may also contain at least one coupler and / or at least one direct dye, in particular for modifying the nuances or enriching them with reflections.
Les coupleurs utilisables dans les compositions de teinture d'oxydation conformes à l'invention peuvent être choisis parmi les coupleurs utilisés de façon classique en teinture d'oxydation et parmi lesquels on peut notamment citer les métaphénylènediamines, les méta-aminophénols, les métadiphénols, les naphtols et les coupleurs hétérocycliques tels que par exemple les dérivés indoliques, les dérivés indoliniques, les dérivés pyridiniques, les dérivés indazoliques, les dérivés de pyrazolo[1 ,5-b]-1 ,2,4-triazole, les dérivés de pyrazolo[3,2-c]-1 ,2,4-triazole, les dérivés de benzimidazole, les dérivés de benzothiazole, les dérivés de benzoxazole, les dérivés de 1 ,3-benzodioxole et les pyrazolones, et leurs sels d'addition avec un acide.The couplers which can be used in the oxidation dye compositions in accordance with the invention can be chosen from the couplers conventionally used in oxidation dyeing and among which there may be mentioned in particular metaphenylenediamines, meta-aminophenols, metadiphenols, naphthols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, pyridine derivatives, indazole derivatives, pyrazolo derivatives [1, 5-b] -1, 2,4-triazole, pyrazolo derivatives [ 3,2-c] -1, 2,4-triazole, benzimidazole derivatives, benzothiazole derivatives, benzoxazole derivatives, 1,3-benzodioxole derivatives and pyrazolones, and their addition salts with a acid.
Ces coupleurs sont plus particulièrement choisis parmi le 2-méthyl 5-amino phénol, le 5-N- (β-hydroxyéthyl)amino 2-méthyl phénol, le 3-amino phénol, le 1 ,3-dihydroxy 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 -méthoxy benzène, le 1 ,3-diamino benzène, le ,3-bis-(2,4-diaminophénoxy) propane, le sésamol, Pα-naphtol, le 2-méthyl-1-naphtol, le 6-hydroxy indole, le 4-hydroxy indole, le 4-hydroxy N-méthyl indole, la 6-hydroxy indoline, la 6-hydroxybenzomorpholine, la 3,5 diamino 2,6diméthoxy pyridine, le 1-N β hydroxyéthylamine 3,4 méthylènedioxy benzène, le 2,6 bis(β hydroxyéthylamino)toluène, la 2,6-dihydroxy 4-méthyl pyridine, le 1-H 3-méthyl pyrazole 5- one, le 1-phényl 3-méthyl pyrazole 5-one, et leurs sels d'addition avec un acide.These couplers are more particularly chosen from 2-methyl 5-amino phenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1, 3-dihydroxy benzene, 1, 3 -dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1 -methoxy benzene, 1, 3-diamino benzene, le, 3-bis- (2,4-diaminophenoxy) propane, sesamol, Pα-naphthol, 2-methyl-1-naphtol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 6-hydroxy indoline, 6-hydroxybenzomorpholine, 3,5 diamino 2,6dimethoxy pyridine, 1-N β hydroxyethylamine 3,4 methylenedioxy benzene, 2,6 bis (β hydroxyethylamino ) toluene, 2,6-dihydroxy 4-methyl pyridine, 1-H 3-methyl pyrazole 5-one, 1-phenyl 3-methyl pyrazole 5-one, and their addition salts with an acid.
Lorsqu'ils sont présents, le ou les coupleurs représentent de préférence de 0,0001 à 10 % en poids environ du poids total de la composition tinctoriale et encore plus préférentiellement de 0,005 à 5 % en poids environ de ce poids.When they are present, the coupler or couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately of this weight.
La composition tinctoriale conforme 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, zwitterioniques ou leurs mélanges, des polymères anioniques, cationiques, non-ioniques, amphotères, zwitterioniques ou leurs mélanges, des agents épaississants minéraux ou organiques, 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, des agents filmogènes, 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 mixtures thereof, anionic, cationic polymers , non-ionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as by example of silicones, film-forming agents, preserving agents, opacifying agents.
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. 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.Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered. by the addition (s) envisaged. The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
Un autre objet de l'invention est l'utilisation des compositions de l'invention pour la teinture d'oxydation des fibres kératiniques, et en particulier des fibres humaines telles que les cheveux.Another subject of the invention is the use of the compositions of the invention for the oxidation dyeing of keratin fibers, and in particular human fibers such as the hair.
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.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 au moins une composition tinctoriale telle que définie précédemment, la couleur étant révélée à pH acide, neutre ou alcalin à l'aide d'un agent oxydant qui est ajouté juste au moment de l'emploi à la composition tinctoriale ou qui est appliqué séparément, simultanément ou séquentiellement.According to this process, at least one dye composition as defined above is applied to the fibers, the color being revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just at the time of use. the dye composition or which is applied separately, simultaneously or sequentially.
Selon une forme de mise en oeuvre préférée du procédé de teinture de l'invention, on mélange de préférence, au moment de l'emploi, la composition tinctoriale décrite ci-dessus avec une composition oxydante contenant, dans un milieu approprié pour la teinture, au moins un agent oxydant présent en une quantité suffisante pour développer une coloration. Le mélange obtenu est ensuite appliqué sur les fibres kératiniques et on laisse poser pendant 3 à 50 minutes environ, de préférerjce 5 à 30 minutes environ, après quoi on rince, on lave au shampooing, on rince à nouveau et on sèche.According to a preferred embodiment of the dyeing process of the invention, the dye composition described above is preferably mixed, at the time of use, with an oxidizing composition containing, in a medium suitable for dyeing, at least one oxidizing agent present in an amount sufficient to develop coloring. The mixture obtained is then applied to the keratin fibers and left to stand for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, washed with shampoo, rinsed again and dried.
L'agent oxydant peut être choisi parmi les agents oxydants classiquement utilisés pour la teinture d'oxydation des fibres kératiniques, et parmi lesquels on peut citer le peroxyde d'hydrogène, le peroxyde d'urée, les bramâtes de métaux alcalins, les persels tels que les perborates et persulfates, et les enzymes parmi lesquelles on peut citer les peroxydases, les oxydo-réductases à 2 électrons telles que les uricases et les oxygénases à 4 électrons comme les laccases. Le peroxyde d'hydrogène est particulièrement préféré.The oxidizing agent can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bramates, persalts such as as perborates and persulfates, and the enzymes among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.
Le pH de la composition oxydante renfermant l'agent oxydant tel que défini ci-dessus 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 préférentiellement entre 5 et 11. Il est 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 as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and again more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.
La composition oxydante telle que définie ci-dessus peut également renfermer divers adjuvants utilisés classiquement dans les compositions pour la teinture des cheveux et tels que définis précédemment.The oxidizing composition as defined above may also contain various adjuvants conventionally used in compositions for dyeing the hair 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 ou tout autre système de conditionnement à plusieurs compartiments dont un premier compartiment renferme la composition tinctoriale telle que définie ci-dessus et un second compartiment renferme la composition oxydante telle que définie ci-dessus. Ces dispositifs peuvent être équipés d'un moyen permettant de délivrer sur les cheveux le mélange souhaité, par tout moyen connu de l'homme du métier, par exemple 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 or any other packaging system with several compartments, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition. as defined above. These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, by any means known to a person skilled in the art, for example the devices described in patent FR-2,586,913 in the name of the applicant.
Enfin, l'invention a également pour objet le produit coloré résultant de l'oxydation d'au moins un composé de formule (I) telle que définie ci-dessus en présence d'au moins un agent oxydant, et éventuellement en présence d'au moins un coupleur et/ou d'au moins une base d'oxydation additionnelle.Finally, the subject of the invention is also the colored product resulting from the oxidation of at least one compound of formula (I) as defined above in the presence of at least one oxidizing agent, and optionally in the presence of at least one coupler and / or at least one additional oxidation base.
Ces produits colorés peuvent également se présenter sous la forme de pigments et être utilisés à titre de colorants directs pour la teinture directe de cheveux ou bien encore être incorporés dans les produits cosmétiques tels que par exemple dans des produits de maquillage. Les exemples qui suivent sont destinés à illustrer l'invention sans toutefois en limiter la portée.These colored products can also be in the form of pigments and be used as direct dyes for the direct dyeing of hair or even be incorporated in cosmetic products such as for example in makeup products. The examples which follow are intended to illustrate the invention without however limiting its scope.
EXEMPLESEXAMPLES
EXEMPLE 1 : Synthèse du chlorhydrate d'acide 1-(4-Amino-phenyl)-3-hydroxy- pyrrolidine-2-carboxylique (2)EXAMPLE 1 Synthesis of 1- (4-Amino-phenyl) -3-hydroxy-pyrrolidine-2-carboxylic acid hydrochloride (2)
synthèse du 3-hydroxy-1-(4-nitro-phenyl)-pyrrolidine-2-carboxylic acid (1 ) : Après dissolution de 17,9 g de 1-fluoro-4-nitrobenzene (0,127 mol) et de 20 g de trans-3- hydroxy-L-proline (0,152 mol) dans 150 ml de N-méthyl pyrrolidone (NMP), on ajoute sous atmosphère d'azote 21.04 g de carbonate de potassium (0,152 mol) et on chauffe à 93°C pendant 3h25. On laisse refroidir, puis on coule le milieu réactionnel dans 600 ml d'une solution aqueuse saturée en chlorure de sodium. On ajoute ensuite goutte à goutte, sous agitation, une solution d'acide chlorhydrique à 10% jusqu'à l'obtention d'une solution à pH=3. Un précipité vert apparaît. Ce dernier est alors filtré, lavé avec 20 ml d'eau puis séché sous pression réduite en présence de P2O5. On obtient ainsi 30,8 g (96%) d'acide 3- hydroxy-1-(4-nitro-phenyl)-pyrrolidine-2-carboxylique (1) sous forme d'un solide vert.synthesis of 3-hydroxy-1- (4-nitro-phenyl) -pyrrolidine-2-carboxylic acid (1): After dissolution of 17.9 g of 1-fluoro-4-nitrobenzene (0.127 mol) and 20 g of trans-3-hydroxy-L-proline (0.152 mol) in 150 ml of N-methyl pyrrolidone (NMP), 21.04 g of potassium carbonate (0.152 mol) are added under a nitrogen atmosphere and the mixture is heated to 93 ° C. for 3:25. The mixture is allowed to cool, then the reaction medium is poured into 600 ml of a saturated aqueous sodium chloride solution. A 10% hydrochloric acid solution is then added dropwise, with stirring, until a solution with pH = 3 is obtained. A green precipitate appears. The latter is then filtered, washed with 20 ml of water and then dried under reduced pressure in the presence of P 2 O 5 . 30.8 g (96%) of 3-hydroxy-1- (4-nitro-phenyl) -pyrrolidine-2-carboxylic acid (1) are thus obtained in the form of a green solid.
- 1 H-RMN (DMSO d6, 200 MHz)- 1 H-NMR (DMSO d6, 200 MHz)
2.22 (m, 2H), 3.8 (m, 2H), 4.42 (m, 1 H), 4.70 (m, 1 H), 5.81 (m, 1 H), 6.80 (d, 2H), 8.30 (d,2.22 (m, 2H), 3.8 (m, 2H), 4.42 (m, 1H), 4.70 (m, 1H), 5.81 (m, 1H), 6.80 (d, 2H), 8.30 (d,
2H)2H)
- synthèse du chlorhydrate de l'acide 1-(4-amino-phenyl)-3-hydroxy- pyrrolidine-2-carboxylique (2) :- synthesis of 1- (4-amino-phenyl) -3-hydroxy-pyrrolidine-2-carboxylic acid hydrochloride (2):
Dans un tricol de 250 ml sous atmosphère d'azote, on introduit sous agitation 6,5 g d'acide 3-hydroxy-1-(4-nitro-phenyl)-pyrrolidine-2-carboxylique (1 ) (25,7 mmol), 4 g de Pd/C à 10% (54% humide), 100 ml d'éthanol, 10 ml d'eau et 70 ml de cyclohexène. Le milieu réactionnel est chauffé au reflux pendant 12 heures jusqu'à la disparition de l'acide 3-hydroxy-1-(4-nitro-phenyl)-pyrrolidine-2-carboxylique (1 ) (contrôlée par CCM : NH4OH: 6 / CH2CI2 47 / MeOH 47). Après refroidissement du milieu, on ajoute une solution aqueuse contenant 7,5 ml d'acide chlorhydrique et 10 ml d'eau. Après filtration du milieu réactionnel et ajout de 100 ml d'isopropanol, le filtrat est concentré sous pression réduite jusqu'à l'obtention d'un précipité. Le solide est filtré, lavé à l'isopropanol et à l'éther éthylique, puis séché sous pression réduite en présence de potasse. On obtient ainsi 5,4 g (71%) de dichlorhydrate d'acide 1-(4-amino-phenyl)-3-hydroxy-pyrrolidine-2- carboxylique (2) sous forme d'un solide beige foncé.6.5 g of 3-hydroxy-1- (4-nitro-phenyl) -pyrrolidine-2-carboxylic acid (1) (25.7 mmol) are introduced into a 250 ml three-necked flask under a nitrogen atmosphere. ), 4 g of 10% Pd / C (54% wet), 100 ml of ethanol, 10 ml of water and 70 ml of cyclohexene. The reaction medium is heated at reflux for 12 hours until the disappearance of the 3-hydroxy-1- (4-nitro-phenyl) -pyrrolidine-2-carboxylic acid (1) (controlled by TLC: NH 4 OH: 6 / CH 2 CI 2 47 / MeOH 47). After the medium has cooled, an aqueous solution containing 7.5 ml of hydrochloric acid and 10 ml of water is added. After filtration of the reaction medium and addition of 100 ml of isopropanol, the filtrate is concentrated under reduced pressure until a precipitate is obtained. The solid is filtered, washed with isopropanol and ethyl ether, then dried under reduced pressure in the presence of potassium hydroxide. 5.4 g (71%) of 1- (4-amino-phenyl) -3-hydroxy-pyrrolidin-2-carboxylic acid dihydrochloride (2) are thus obtained in the form of a dark beige solid.
- 1 H-RMN (DMSO d6, 500 MHz)- 1 H-NMR (DMSO d6, 500 MHz)
2.08-2.27 (m, 2H), 3.50-3.63 (m, 2H), 4.23 (s, 1 H), 4.69 (s, 1 H), 6.70 (d, 2H), 7.28 (d, 2H)2.08-2.27 (m, 2H), 3.50-3.63 (m, 2H), 4.23 (s, 1 H), 4.69 (s, 1 H), 6.70 (d, 2H), 7.28 (d, 2H)
Spectre de masse : spectre en accord avec la structureMass spectrum: spectrum in agreement with the structure
Analyse élémentaire (PM = 295.164 ; dιH14N2O3.2HCI)Elementary analysis (PM = 295.164; dιH 14 N 2 O 3 .2HCI)
EXEMPLE 2 : Synthèse dichlorhydrate de 1-(4-Amino-phenyl)-2- hydroxymethyl-pyrrolidin-3-ol (4)EXAMPLE 2 Synthesis of 1- (4-Amino-phenyl) -2-hydroxymethyl-pyrrolidin-3-ol (4) dihydrochloride
- Synthèse du 2-hydroxyméthyl-1-(4-nitro-phényl)-pyrrolidin-3-ol 3 :- Synthesis of 2-hydroxymethyl-1- (4-nitro-phenyl) -pyrrolidin-3-ol 3:
A une solution hétérogène contenant 10 g d'acide 3-hydroxy-1-(4-nitro-phenyl)-pyrrolidine- 2-carboxylique (1) (39,6 mmol) et 75 ml de THF, on ajoute sous atmosphère d'azote goutte à goutte 118,8 ml d'une solution 1M de BH3.THF dans le THF (118,8 mmol) et on agite le milieu réactionnel à température ambiante pendant 16 heures (le milieu devient homogène au bout de 9 heures). On ajoute ensuite lentement 300 ml de méthanol puis on évapore le milieu réactionnel jusqu'à l'obtention d'une solide jaune. On met en suspension le solide résultant dans une solution aqueuse contenant 15% massique de chlorure de sodium puis on filtre et lave le solide avec une solution de chlorure de sodium à 10%. Le solide est ensuite chauffé sous vide en présence de P2O5. On obtient ainsi 9,2 g (97,5%) de 2-hydroxyméthyl-1-(4-nitro-phényl)-pyrrolidin-3-ol (3) sous forme d'un solide orange.To a heterogeneous solution containing 10 g of 3-hydroxy-1- (4-nitro-phenyl) -pyrrolidine- 2-carboxylic acid (1) (39.6 mmol) and 75 ml of THF, the following are added under an atmosphere of nitrogen drop by drop 118.8 ml of a 1M solution of BH3.THF in THF (118.8 mmol) and the reaction medium is stirred at room temperature for 16 hours (the medium becomes homogeneous after 9 hours). 300 ml of methanol are then added slowly and then the reaction medium is evaporated until a yellow solid is obtained. The resulting solid is suspended in an aqueous solution containing 15% by mass of sodium chloride, then the solid is filtered and washed with a 10% solution of sodium chloride. The solid is then heated under vacuum in the presence of P 2 O 5 . 9.2 g (97.5%) of 2-hydroxymethyl-1- (4-nitro-phenyl) -pyrrolidin-3-ol (3) are thus obtained in the form of an orange solid.
- 1 H-RMN (DMSO d6, 200 MHz)- 1 H-NMR (DMSO d6, 200 MHz)
1.76-1.85 (m, 1 H), 2.06-2.13 (m, 1 H), 3.12-3.20 (m, 1H), 3.33-3.45 (m, 2H), 3.59-3.64 (m,1.76-1.85 (m, 1 H), 2.06-2.13 (m, 1 H), 3.12-3.20 (m, 1H), 3.33-3.45 (m, 2H), 3.59-3.64 (m,
1 H), 4.21-4.24 (m, 1 H), 4.89-4.97 (m, 2H), 6.60 (d, 2H), 7.98 (d, 2H)1 H), 4.21-4.24 (m, 1 H), 4.89-4.97 (m, 2H), 6.60 (d, 2H), 7.98 (d, 2H)
- synthèse du dichlorhydrate de 1-(4-Amino-phenyl)-2-hydroxymethyl-pyrrolidin-3-ol (4): Dans un réacteur à hydrogéner en inox, on dissout partiellement 16 g de 2-hydroxymethyl- 1-(4-nitro-phenyl)-pyrrolidin-3-ol 3 (67,1 mmol) dans 200 ml de méthanol. On ajoute 4 g de Pd/C à 5 % (50% humide), on ferme le réacteur et le purge à l'azote 3 fois sous agitation (1800 tour/min). On introduit ensuite l'hydrogène sous une pression de 5-6 bars à température ambiante. La température monte jusqu'à 35°C puis, au bout d'1h15 redescend à 27°C. Le réacteur est alors purgé à l'azote et le milieu réactionnel est filtré sous atmosphère d'azote et le filtrat est récupéré immédiatement dans une solution contenant 20 ml d'acide chlorhydrique à 37% et 180 ml d'isopropanol. Le filtrat est ensuite concentré jusqu'à l'obtention d'un précipité. Le solide est filtré, lavé à l'isopropanol puis à l'éther éthylique et séché sous vide en présence de potasse. On obtient ainsi 15,65 g (83%) de dichlorhydrate de1-(4-Amino-phényl)-2-hydroxyméthyl-pyrrolidin-3-ol, (4) sous forme d'un solide blanc.- synthesis of 1- (4-Amino-phenyl) -2-hydroxymethyl-pyrrolidin-3-ol (4) dihydrochloride: 16 g of 2-hydroxymethyl- 1- (4) are partially dissolved in a stainless steel hydrogenating reactor -nitro-phenyl) -pyrrolidin-3-ol 3 (67.1 mmol) in 200 ml of methanol. 4 g of 5% Pd / C (50% wet) are added, the reactor is closed and purged with nitrogen 3 times with stirring (1800 rpm). The hydrogen is then introduced under a pressure of 5-6 bars at room temperature. The temperature rises to 35 ° C then, after 1 hour 15 minutes, drops to 27 ° C. The reactor is then purged with nitrogen and the reaction medium is filtered under a nitrogen atmosphere and the filtrate is immediately recovered in a solution containing 20 ml of 37% hydrochloric acid and 180 ml of isopropanol. The filtrate is then concentrated until a precipitate is obtained. The solid is filtered, washed with isopropanol then with ethyl ether and dried under vacuum in the presence of potassium hydroxide. 15.65 g (83%) of 1- (4-Amino-phenyl) -2-hydroxymethyl-pyrrolidin-3-ol dihydrochloride (4) are thus obtained in the form of a white solid.
- 1 H-RMN (DMSO d6, 500 MHz)- 1 H-NMR (DMSO d6, 500 MHz)
2.21-2.26 (m, 1 H), 2.40-2.43 (m, 1 H), 3.70-3.90 (m, 5H), 4.54-4.56 (m, 1 H), 7.44 (m, 2H),2.21-2.26 (m, 1 H), 2.40-2.43 (m, 1 H), 3.70-3.90 (m, 5H), 4.54-4.56 (m, 1 H), 7.44 (m, 2H),
7.53 (m, 2H)7.53 (m, 2H)
• Spectre de masse : spectre en accord avec la structure • • Mass spectrum: spectrum in agreement with the structure •
• Analyse élémentaire (PM = 281.181 ; C-πH^NsOa^HCI)• Elementary analysis (PM = 281.181; C-πH ^ NsOa ^ HCI)
EXEMPLE 3 : Compositions tinctorialesEXAMPLE 3: Dye compositions
On a préparé les compositions tinctoriales conformes à l'invention suivantes The following dye compositions according to the invention were prepared
(*) Support de teinture commun :(*) Common dye support:
- Alcool oléique polyglycérolé à 2 moles de glycérol 4,0 g - Alcool oléique polyglycérolé à 4 moles de glycérol, à 78 % de matières actives (M.Â.) 5,69 g M.A- Polyglycerolated oleic alcohol with 2 moles of glycerol 4.0 g - Polyglycerolated oleic alcohol with 4 moles of glycerol, 78% active ingredient (M.A.) 5.69 g M.A
- Acide oléique 3,0 g- Oleic acid 3.0 g
- Aminé oléique à 2 moles d'oxyde d'éthylène vendue sous la dénomination commerciale ETHOMEEN 012 ® par la société AKZO 7,0 g - Laurylamino succinamate de diéthylaminopropyle, sel de sodium à 55 % de M.A. 3,0 g M.A- Oleic amine containing 2 moles of ethylene oxide sold under the trade name ETHOMEEN 012® by the company AKZO 7.0 g - Laurylamino diethylaminopropyl succinamate, sodium salt at 55% of M.A. 3.0 g M.A
- Alcool oléique 5,0 g- Oleic alcohol 5.0 g
- Diéthanolamide d'acide oléique 12,0 g- Oleic acid diethanolamide 12.0 g
- Propylèneglycol 3,5 g - Alcool éthylique 7,0 g- Propylene glycol 3.5 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 - Antioxydant, séquestrant q.s.- Ammonium acetate 0.8 g - Antioxidant, sequestering q.s.
- Parfum, conservateur q.s.- Perfume, preservative q.s.
- Ammoniaque à 20 % de NH3 10,0 g- Ammonia at 20% NH 3 10.0 g
Au moment de l'emploi, on mélange chaque composition tinctoriale avec une quantité égale d'une composition oxydante constituée par une solution d'eau oxygénée à 20 volumes (6 % en poids) et présentant un pH d'environ 3.At the time of use, each dye composition is mixed with an equal amount of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight) and having a pH of approximately 3.
Chaque mélange obtenu présente un pH d'environ 9,5 et est appliqué pendant 30 minutes sur des mèches de cheveux gris naturels à 90 % de blancs. Les mèches de cheveux sont ensuite rincées, lavées avec un shampooing standard puis séchées.Each mixture obtained has a pH of approximately 9.5 and is applied for 30 minutes to locks of natural gray hair containing 90% white hairs. The locks of hair are then rinsed, washed with a standard shampoo and then dried.
Les mèches de cheveux ont été teintes dans les nuances figurant dans le tableau ci-dessous : The locks of hair were dyed in the shades shown in the table below:

Claims

REVENDICATIONS
1. Composition pour la teinture d'oxydation des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, comprenant, dans un milieu approprié pour la teinture,1. Composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing,
- au moins une base d'oxydation choisie parmi les composés de formule (I) suivante, et/ou leurs sels d'addition avec un acide- at least one oxidation base chosen from the compounds of formula (I) below, and / or their addition salts with an acid
dans laquelle : in which :
- Ri représente un atome d'halogène ; une chaîne carbonée en C-ι-C7, saturée ou pouvant contenir une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples, linéaire ou ramifiée pouvant être sous forme de cycle ayant de 3 à 6 chaînons, un ou plusieurs atomes de carbone de la chaîne pouvant être remplacés par un atome d'oxygène, d'azote ou de soufre, par un groupe SO2 ou par un atome d'halogène, le radical R. ne comportant pas de liaison peroxyde, ni de radicaux diazo, nitro ou nitroso ;- Ri represents a halogen atom; a C-ι-C 7 carbon chain, saturated or which may contain one or more double bonds and / or one or more triple bonds, linear or branched, which may be in the form of a ring having 3 to 6 members, one or more atoms of carbon chain may be replaced by an oxygen, nitrogen or sulfur, with an SO 2 group or by a halogen atom, the radical R. containing no peroxide bond, nor diazo, nitro or nitroso radicals;
- R3 et R représentent, indépendamment l'un de l'autre un radical hydroxy ; un radical amino ; une chaîne carbonée en C C saturée ou insaturée ; un radical -OR6 dans lequel R6 représente un radical alkyle en C C4 pouvant être substitué par un ou plusieurs radicaux choisis dans le groupe constitué par un atome d'halogène, un radical hydroxy, alcoxy en C C2, amino ou aminoalkyle en d-C2 ; un radical -NR7R8 dans lequel R et R8 représentent indépendamment l'un de l'autre un atome d'hydrogène, un radical alkyle en C C4, un radical alkyle en d-C4 substitué par un ou plusieurs radicaux choisis dans le groupe constitué par un atome d'halogène, un radical hydroxy, alcoxy en C C2, amino ou aminoalkyle en C C2.- R 3 and R represent, independently of one another, a hydroxy radical; an amino radical; a carbon chain in saturated or unsaturated CC; a radical -OR 6 in which R 6 represents an alkyl radical in CC 4 which may be substituted by one or more radicals chosen from the group consisting of a halogen atom, a hydroxy radical, alkoxy in CC 2 , amino or aminoalkyl in dC 2 ; a radical -NR 7 R 8 in which R and R 8 independently of one another represent a hydrogen atom, an alkyl radical in CC 4 , an alkyl radical in dC 4 substituted by one or more radicals chosen from the group consisting of a halogen atom, a hydroxy, CC 2 alkoxy, amino or CC 2 aminoalkyl radical.
- R2 et R5 représentent, indépendamment l'un de l'autre, une chaîne carbonée en Cι-C4, saturée ou insaturée ; un radical alkyle en C C4 substitué par un radical alcoxy en C-ι-C4, acétoxy, amino, carboxyle, carbamoyie, (mono ou dialkyl)(C C4)carbamoyle, alkoxy(CrC )carbonyle, monohydroxyalcoxy en C C6 ou par polyhydroxyalcoxy en C -C6 ; un radical monohydroxyalkyle en C-ι-C4 ; un radical polyhydroxyalkyle en C-ι-C6 ; un radical aminoalkyle en C1-C4 dont l'aminé est mono ou disubstituée par un radical alkyle en d- C , acétyle, monohydroxyalkyle en C C4 ou polyhydroxyalkyle en C2-C6 ; un radical polyaminoalkyle en C2-C4 ; un radical alkyle en C2-C4 substitué par au moins un groupe amino et au moins un groupe hydroxy ; un radical carboxyle ; un radical carbamoyie ; un radical (mono ou dialkyl)(Cι-C4)carbamoyle ; un radical alkoxy(d-C4)carbonyle ; un radical alkyl (C1-C4)carbonyle, - R4 et R5 peuvent aussi représenter indépendamment l'un de l'autre un atome d'hydrogène- R 2 and R 5 represent, independently of one another, a carbon chain in Cι-C 4 , saturated or unsaturated; a CC 4 alkyl radical substituted by an alkoxy radical in C-ι-C 4 , acetoxy, amino, carboxyl, carbamoyie, (mono or dialkyl) (CC 4 ) carbamoyl, alkoxy (CrC) carbonyl, monohydroxyalkoxy in CC 6 or by polyhydroxyalkoxy in C -C 6 ; a C-ι-C 4 monohydroxyalkyl radical; a C-ι-C 6 polyhydroxyalkyl radical; an aminoalkyl radical in C1-C4 whose amine is mono- or disubstituted with alkyl d- C, acetyl, monohydroxyalkyl or polyhydroxyalkyl 4 CC C 2 -C 6; a C 2 -C 4 polyaminoalkyl radical; a C 2 -C 4 alkyl radical substituted by at least one amino group and at least one hydroxy group; a carboxyl radical; a carbamoyie radical; a radical (mono or dialkyl) (Cι-C 4 ) carbamoyl; an alkoxy (dC 4 ) carbonyl radical; a (C1-C4) carbonyl alkyl radical, - R 4 and R 5 can also represent, independently of one another, a hydrogen atom
- n est compris entre 0 et 2, étant entendu que lorsque n est égal à 2 alors les radicaux Ri peuvent être identiques ou différents- n is between 0 and 2, it being understood that when n is equal to 2 then the radicals Ri can be identical or different
2. Composition selon la revendication 1 , dans laquelle le radical Ri de la formule (I) est choisi de parmi un atome de chlore ou de brome, un radical méthyle, éthyle, isopropyle, vinyle, allyle, méthoxyméthyle, hydroxyméthyle, 1-carboxyméthyle, 1- aminométhyle, 2-carboxyéthyle, 2-hydroxyéthyle, 3-hydroxypropyle, 1 ,2-dihydroxyéthyle, 1-hydroxy-2-aminoéthyle, 1-amino-2-hydroxyéthyle, 1 ,2-diaminoéthyle, méthoxy, éthoxy, allyloxy, 2-hydroxyéthyloxy.2. Composition according to Claim 1, in which the radical R 1 of formula (I) is chosen from a chlorine or bromine atom, a methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl radical. , 1- aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl, 1, 2-diaminoethyl, methoxy, ethoxy, allyloxy , 2-hydroxyethyloxy.
3. Composition selon la revendication 1 ou 2, dans laquelle les radicaux R2 et R5 sont choisis parmi le radical hydroxyméthyle, le radical aminométhyle, le radical carboxyle, le radical carbamoyie, le radical 2-hydroxyéthyloxyméthyle, le radical 2- hydroxyéthylaminométhyle, et l'hydrogène pour R5.3. Composition according to claim 1 or 2, in which the radicals R 2 and R 5 are chosen from the hydroxymethyl radical, the aminomethyl radical, the carboxyl radical, the carbamoyie radical, the 2-hydroxyethyloxymethyl radical, the 2-hydroxyethylaminomethyl radical, and hydrogen for R 5 .
4. Composition selon la revendication 1 , 2 ou 3, dans laquelle R3 et R4 sont choisis parmi le radical hydroxyle, le radical acétoxy, le radical amino, le radical méthylamino, le radical diméthylamino, le radical 2-hydroxyéthylamino, le radical 2- hydroxyéthyloxy, et l'hydrogène pour R4 4. Composition according to claim 1, 2 or 3, in which R 3 and R 4 are chosen from the hydroxyl radical, the acetoxy radical, the amino radical, the methylamino radical, the dimethylamino radical, the 2-hydroxyethylamino radical, the radical 2- hydroxyethyloxy, and hydrogen for R 4
5. Composition selon l'une quelconque des revendications 1 à 4 dans laquelle n est 0 ou 1.5. Composition according to any one of claims 1 to 4 in which n is 0 or 1.
6. Composition selon l'une quelconque des revendications 1 à 5, dans laquelle le composé de formule (I) est choisi dans le groupe constitué par : 6. Composition according to any one of claims 1 to 5, in which the compound of formula (I) is chosen from the group consisting of:
et leurs sels d'addition avec un acide.and their addition salts with an acid.
7. Composition selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le ou les composés de formule (I) représentent de 0,0005 à 12 % en poids du poids total de la composition tinctoriale.7. Composition according to any one of claims 1 to 6, characterized in that the compound or compounds of formula (I) represent from 0.0005 to 12% by weight of the total weight of the dye composition.
8. Composition selon l'une quelconque des revendications 1 à 7, caractérisée en ce qu'elle contient, en plus du ou des composés de formule (I), au moins une base d'oxydation additionnelle choisie parmi les paraphénylènediamines différentes des composés de formule (I), les bis-phénylalkylènediamines, les para-aminophénols, les ortho-aminophénols et les bases hétérocycliques.8. Composition according to any one of claims 1 to 7, characterized in that it contains, in addition to the compound or compounds of formula (I), at least one base additional oxidation chosen from paraphenylenediamines different from the compounds of formula (I), bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
9. Composition selon l'une quelconque des revendications 1 à 8, caractérisée en ce que la ou les bases d'oxydation additionnelles représentent de 0,0005 à 12 % en poids du poids total de la composition tinctoriale.9. Composition according to any one of claims 1 to 8, characterized in that the additional oxidation base (s) represent from 0.0005 to 12% by weight of the total weight of the dye composition.
10. Composition selon l'une quelconque des revendications 1 à 9, caractérisée en ce qu'elle contient au moins un coupleur et/ou au moins un colorant direct.10. Composition according to any one of claims 1 to 9, characterized in that it contains at least one coupler and / or at least one direct dye.
11. Composition selon la revendication 10, caractérisée en ce que les coupleurs sont choisis parmi les métaphénylènediamines, les méta-aminophénols, les métadiphénols, les naphtols et les coupleurs hétérocycliques.11. Composition according to claim 10, characterized in that the couplers are chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthols and heterocyclic couplers.
12. Composition selon l'une quelconque des revendications 10 et 11 , caractérisée en ce que le ou les coupleurs représentent de 0,0001 à 10 % en poids du poids total de la composition tinctoriale.12. Composition according to any one of claims 10 and 11, characterized in that the coupler (s) represent from 0.0001 to 10% by weight of the total weight of the dye composition.
13. Composition selon l'une quelconque des revendications 1 à 12, caractérisée en ce que les sels d'addition avec un acide du composés de formule (I) sont choisis parmi les chlorhydrates, les bromhydrates, les sulfates, les citrates, les succinates, les tartrates, les lactates et les acétates.13. Composition according to any one of claims 1 to 12, characterized in that the addition salts with an acid of the compounds of formula (I) are chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates , tartrates, lactates and acetates.
14. Utilisation de la composition selon l'une quelconque des revendications 1 à14. Use of the composition according to any one of claims 1 to
13 pour la teinture d'oxydation des fibres kératiniques, et en particulier des fibres humaines telles que les cheveux.13 for the oxidation dyeing of keratin fibers, and in particular human fibers such as the hair.
15. Procédé de teinture d'oxydation des fibres kératiniques et en particulier des fibres kératiniques humaines telles que les cheveux, caractérisé en ce qu'on applique sur les fibres la composition telle que définie à l'une quelconque des revendications 1 à 13, et un agent oxydant, l'agent oxydant étant ajouté au moment de l'emploi à la composition ou appliqué sur les fibres séparément, simultanément ou séquentiellement.15. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that the composition as defined in any one of claims 1 to 13 is applied to the fibers, and an oxidizing agent, the oxidizing agent being added at the time of use to the composition or applied to the fibers separately, simultaneously or sequentially.
16. Procédé selon la revendication 15, caractérisé en ce que l'agent oxydant est choisi parmi le peroxyde d'hydrogène, le peroxyde d'urée, les bromates de métaux alcalins, les persels, les peracides, et les enzymes d'oxydo réduction. 16. The method of claim 15, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids, and redox enzymes .
17. Dispositif à plusieurs compartiments comprenant un premier compartiment renfermant une composition telle que définie à l'une quelconque des revendications 1 à 13 et un second compartiment renfermant une composition oxydante.17. Multi-compartment device comprising a first compartment containing a composition as defined in any one of claims 1 to 13 and a second compartment containing an oxidizing composition.
18. Produit coloré susceptible d'être obtenu par réaction de la composition telle que défini selon l'une quelconque des revendications 1 à 13 avec un agent oxydant. 18. A colored product capable of being obtained by reaction of the composition as defined according to any one of claims 1 to 13 with an oxidizing agent.
EP01999348A 2000-12-06 2001-11-13 Dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted at least in positions 2 and 3 Withdrawn EP1341508A1 (en)

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FR0015842A FR2817472B1 (en) 2000-12-06 2000-12-06 OXIDATION DYEING COMPOSITION BASED ON 1- (4-AMINOPHENYL) PYRROLIDINES SUBSTITUTED AT LEAST 2 AND 3 AND DYEING METHOD THEREOF
FR0015842 2000-12-06
PCT/FR2001/003541 WO2002045669A1 (en) 2000-12-06 2001-11-13 Dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted at least in positions 2 and 3

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FR2817472B1 (en) 2003-01-03
FR2817472A1 (en) 2002-06-07
AU2002221983A1 (en) 2002-06-18
AR031777A1 (en) 2003-10-01
US20040083559A1 (en) 2004-05-06

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