Classifications

• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/38—Nitrogen atoms

Definitions

• the subject of the invention is new 5-substituted 3,4-diamino pyrazole compounds, their methods of preparation, the compositions for oxidation dyeing of keratin fibers containing them as oxidation base as well as the dyeing methods. using this composition.
• oxidation dye precursors in particular ortho or paraphenylenediamines, ortho or paraaminophenols, heterocyclic compounds such as diaminopyrazole derivatives, called generally oxidation bases.
• oxidation dye precursors in particular ortho or paraphenylenediamines, ortho or paraaminophenols, heterocyclic compounds such as diaminopyrazole derivatives, called generally 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 the white hair, and finally to be the least selective possible, that is to say allow to obtain the smallest possible discoloration variations throughout a same keratmic fiber, which can be in fact differently sensitized (ie damaged) between its tip and its root
• Para-aminophenol is usually used, alone or in admixture with other bases, and in combination with suitable couplers, to obtain blue shades, para-phenylenediamines are generally used.
• the first object of the invention therefore is therefore new 5-substituted 3,4-diamino pyrazole compounds of formula (I) as well as their addition salts with an acid:
• Y in which m and n are integers, identical or different, between 1 and 3 inclusive, X represents an oxygen atom or else the NH group, Y represents a hydrogen atom or a methyl radical, and Z represents a methyl radical, an OR or NRR 'group in which R and R', which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical;
• R 3 may represent an amino or C 1 -C 4 alkylamino radical
• - R ⁇ represents an alkyl radical in 0, -0 6 , linear or branched; a C 1 -C 4 hydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted by a halogen atom or an alkyl C, -C 4 alkoxy, C, -C 4 alkyl, nitro, trifluoromethyl, amino or alkylamino, C r C 4; a benzyl radical; a benzyl radical substituted by a halogen atom or an alkyl C, -C 4 alkoxy, C, -C 4 alkyl, nitro, trifluoromethyl, amino or alkylamino, C, -C 4 alkyl; a heterocycle chosen from thiophene, furan and pyridine, or a radical - (CH 2 ) p -0- (CH 2 ) q -0R ", in which
• At least one of the radicals R 4 and R 5 represents a hydrogen atom
• R 2 represents a substituted or unsubstituted phenyl radical, or a benzyl radical or a radical - (CH 2 ) ⁇ X - (CH) - ZY then R 3 , respectively R 5 , cannot represent any of these three radicals,
• - R can also represent a heterocyclic residue 2, 3 or 4-pyridyl, 2 or 3-thienyl, 2 or 3-furyl optionally substituted by a methyl radical.
• addition salts with an acid which can be used in the context of the dye compositions of the invention are in particular chosen from the hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates.
• the subject of the invention is also the processes for preparing the new compounds of formula (I).
• R 1 represents a hydrogen atom
• method A preferably using the following synthetic scheme is used:
• PROCESS A consisting in reacting, in a first step, a ⁇ -ketonitrile ⁇ with hydrazine ⁇ , at a temperature generally greater than 90 ° C, and preferably between 95 and 150 ° C, in an alcoholic solvent to obtain 3 -aminopyrazole ®.
• the 3-aminopyrazole (D is then acetylated in position 3 to lead to 3-acetamidopyrazole ® which is itself nitrated in position 4 then hydrogenated and deacetylated to give the 3,4-diaminopyrazole of formula (IA).
• the nitration of ⁇ is carried out using fuming nitric acid in concentrated sulfuric medium at a temperature between 0 and 5 ° C.
• n-propanol 1-butanol, 2-butanol, 2-methyl 1-butanol, 3-methyl 1-butanol, 2-methyl 1-propanol, n-pentanol, 2-pentanol, 3-methyl 3-pentanol, 4-methyl 2-pentanol or even 2-ethyl 1-butanol.
• the catalytic hydrogenation of the compound ⁇ is preferably carried out in a lower alcohol, in the presence of a catalyst such as palladium on charcoal, at a temperature generally between 20 and 100 ° C.
• a catalyst such as palladium on charcoal
• the deacetylation of the compound ⁇ is preferably carried out in hydrochloric acid at a temperature generally between 40 and 100 ° C.
• method B preferably corresponds to the following synthetic scheme:
• the bases used are generally and preferably the carbonate or hydrogen carbonate salts such as those of lithium, sodium or potassium, or else the organic bases of the family of aliphatic or aromatic amines such as triethylamine, N-methylmorpholine, morpholine, methyldiethylamine, pyridine, 4-dimethylaminopyridine.
• the compound ® is reacted with an aliphatic halide of the chloro-, bromo- or iodo-alkyl class, at a temperature generally between 10 and 100 ° C. in an aprotic solvent of the ethers class Linear or branched aliphatics to lead to a mixture of 5-benzoylaminopyrazole (D and 3-benzoyiaminopyrazole ®.
• the separation of the two regio-isomers CD and ® is preferably carried out either by chromatography on silica gel or by optionally fractionated recrystallization.
• the compound ⁇ is nitrated with fuming nitric acid in concentrated sulfuric medium at a temperature between 0 and 5 ° C to yield the compound ®.
• the compound ® is debenzoylated in the presence of concentrated hydrochloric acid at a temperature preferably between 40 and 100 ° C to yield 3-amino-4-nitropyrazole Q.
• the compound V) is reduced by catalytic hydrogenation in a lower alcohol in the presence of a catalyst such as palladium on carbon at a temperature preferably between 20 and 100 ° C to yield 3,4-diaminopyrazole of formula (IB).
• the subject of the invention is also a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing, at least one 5-substituted 3,4-diamino pyrazole of formula (I) as defined above as an oxidation base and / or at least one of its addition salts with an acid.
• the 5-substituted 3,4-diamino pyrazole (s) of formula (I) above as well as their acid addition salts 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 of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water.
• organic solvent mention may, for example, be made of lower C 1 -C 4 alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol 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 compounds of formula (II) below:
• W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical
• R 8, R 9, R 10 and R represent a hydrogen atom, an alkyl radical in C 1 -C 4 hydroxyalkyl or C, -C 4.
• the dye composition in accordance with the invention may also contain, in addition to the dyes defined above, at least one additional oxidation base different from the 5-substituted 3,4-diamino pyrazoles used in accordance with the invention, which may be chosen from the oxidation bases conventionally used in oxidation dyeing and among which mention may be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
• para-aminophenol examples include para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- ( ⁇ -hydroxyethyl aminomethyl) phenol, and their addition salts with an acid.
• the heterocyclic bases that may be mentioned more particularly by way of example, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives.
• 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, heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, pyridine derivatives and pyrazolones, naphthalene derivatives such as monohydroxynaphthalenes and dihydroxynaphthalenes, and their addition salts with an acid.
• couplers are more particularly chosen from 1, 3-diaminobenzene, le. 2,4-diamino 1- ( ⁇ -hydroxyethyloxy) benzene, 1-methoxy 2-amino 4- ( ⁇ -hydroxyethyl) amino benzene, 4,6- bis- (2-hydroxyethoxy) 1, 3-diaminobenzene, 3-aminophenol, 1-methyl 2-hydroxy 4-amino benzene, 1-methyl 2-hydroxy 4- (2-hydroxyethyl) amino benzene, 1, 3-dihydroxybenzene, 1, 3-dihydroxy 4-chloro benzene , 1, 3-dihydroxy 2-methyl benzene, 6-hydroxybenzomorpholine, 1- ( ⁇ -hydroxyethyl) amino 3,4-methylenedioxy benzene, 6-hydroxyindole, 1, 2-methylenedioxy ⁇ -methoxy 4-amino benzene, 4-hydroxybenzimidazole, and their addition salts with an acid.
• these 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 according to the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers , nonionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example 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 , nonionic, amphoteric, zwitterionic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such
• the dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.
• the invention also relates to a process for dyeing keratin fibers and in particular human keratin fibers such as hair using the dye composition as defined above.
• At least one dye composition as defined above is applied to the fibers, for a time sufficient to develop the desired coloration, either in air or using an oxidizing agent.
• the coloring of the fibers can be carried out without the addition of an oxidizing agent, only in contact with the oxygen in the air.
• the dye composition may then optionally contain oxidation catalysts, in order to accelerate the oxidation process.
• Examples of such compounds are manganese diacetate tetrahydrate, manganese dichloride and its hydrates, manganese dihydrogen carbonate, manganese acetylacetonate, manganese triacetate and its hydrates, manganese trichloride, zinc dichloride, zinc diacetate dihydrate, zinc carbonate, zinc dinitrate, zinc sulfate, iron dichloride, iron sulfate, iron diacetate, cobalt diacetate tetrahydrate, cobalt carbonate, cobalt dichloride , cobalt dinitrate, cobalt sulfate heptahydrate, cupric chloride, ammoniacal silver nitrate.
• Manganese salts are particularly preferred.
• these metal salts are generally used in proportions varying between 0.001 and 4% by weight of metal equivalent per relative to the total weight of the dye composition and preferably between 0.005 and 2% by weight of metal equivalent relative to the total weight of the dye composition
• 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 to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately
• the dye composition described above is preferably mixed with an oxidizing composition containing, in a medium suitable for dyeing, at the time of use, at least one oxidizing agent present in an amount sufficient to develop a coloration
• an oxidizing composition containing, in a medium suitable for dyeing, at the time of use, at least one oxidizing agent present in an amount sufficient to develop a coloration
• the mixture obtained is then applied to the keratin fibers and left to stand for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, washed with shampoo, rinse again and dry
• the oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, peroxide of urea, alkali metal bromates, persalts such as perborates and persulfates 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, such as the devices described in patent FR-2,586,913 in the name of the applicant.
• the suspension was placed in a hydrogenator, under a pressure of 20 bars of hydrogen, at 30 ° C, for 4 hours with vigorous stirring.
• each dye composition 1, 2 or 3 was mixed with an equal amount by weight of an oxidizing composition consisting of a solution of hydrogen peroxide at 20 volumes (6% by weight).
• Each resulting composition was applied for 30 minutes to locks of natural gray hair containing 90% white hairs, permanent or not, at a rate of 28 g per 3 g of hair.
• the locks of hair were then rinsed, washed with a standard shampoo and then dried.
• the color of the locks was evaluated in the MUNSELL system, using a CM 2002 MINOLTA colorimeter.
• a color is defined by the expression HV / C in which the three parameters respectively designate the hue or Hue (H), intensity or Value (V) and purity or Chromaticity (C), the slash in this expression is simply a convention and does not indicate a ratio.
• a test of resistance to light (Xenotest) is carried out on locks of natural or permanent hair dyed according to the dyeing method described above.
• the dyed hair strands were fixed on a support (cardboard or plastic). These supports were placed on sample holders which were rotated around a Xenon lamp for a period of 40 hours at a relative humidity of 25 ⁇ 5% and at a temperature of 42.5 ⁇ 2.5 ° C.
• the color of the locks was evaluated in the MUNSELL system, before and after the test of resistance to light, by means of a CM 2002 MINOLTA colo ⁇ metre.
• ⁇ E represents the difference in color between two wicks
• ⁇ H, ⁇ V and ⁇ C represent the variation in absolute value of the parameters H, V and C
• Co represents the purity of the wick with respect to which it is desired to evaluate the difference color (purity of the wick before the test)
• SE represents the difference in color between two wicks
• ⁇ H, ⁇ V and ⁇ C represent the variation in absolute value of the parameters H, V and C and C 0 represents the purity of the wick with respect to which one wishes to evaluate the difference of color.
• SE therefore reflects the increase in dye obtained, which is all the greater the higher the value of SE.
• the color of the locks was evaluated in the MUNSELL system, using a CM 2002 MINOLTA colorimeter.
• Example 1 containing 3,4-diamino 1,5-dimethyl pyrazole, dihydrochloride
• each dye composition 4 and 5 was mixed with an equal amount by weight of an oxidizing composition constituted by a solution of hydrogen peroxide at 20 volumes (6% by weight), and whose pH had was adjusted between 1 and 1.5 by 2.5 g of orthophosphoric acid per 100 g of hydrogen peroxide.
• Each resulting composition was applied for 30 minutes to locks of natural gray hair containing 90% white hairs, permanent or not, at a rate of 28 g per 3 g of hair.
• the locks of hair were then rinsed, washed with a standard shampoo and then dried.
• the color of the locks was evaluated in the MUNSELL system, using a CM 2002 MINOLTA colorimeter.

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• 1996
  • 1996-05-03 FR FR9605579A patent/FR2748274B1/fr not_active Expired - Fee Related
• 1997
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  • 1997-04-25 JP JP53957697A patent/JP3280987B2/ja not_active Expired - Fee Related
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  • 1997-04-25 CA CA002253898A patent/CA2253898A1/fr not_active Abandoned
  • 1997-04-25 EP EP97921892A patent/EP0900206A1/fr not_active Withdrawn
  • 1997-04-25 WO PCT/FR1997/000750 patent/WO1997042173A1/fr not_active Application Discontinuation
  • 1997-04-30 AR ARP970101785A patent/AR007770A1/es unknown

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