Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
  • C07D213/72—Nitrogen atoms
  • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
  • C07D213/77—Hydrazine radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/86—Hydrazides; Thio or imino analogues thereof
  • C07D213/87—Hydrazides; Thio or imino analogues thereof in position 3
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
  • C07D233/88—Nitrogen atoms, e.g. allantoin
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
  • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
  • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D237/20—Nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
  • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
  • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D237/22—Nitrogen and oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B50/00—Formazane dyes; Tetrazolium dyes
  • C09B50/10—Cationic formazan dyes

Definitions

• the present invention relates to the field of dyeing keratin fibers, it relates more particularly to the use as direct dye of at least one tetraazapentamethine compound, a dye composition comprising at least one such compound, as well as a process for dyeing keratin fibers in which at least one composition comprising such a compound is applied.
• the present invention also relates to new tetraazapentamethine compounds, as well as to their process of preparation.
• oxidation bases such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds.
• oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, give rise, through a process of oxidative condensation, to colored compounds.
• couplers or color modifiers the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.
• This oxidation dyeing process consists in applying to the keratin fibers, oxidation bases or a mixture of oxidation bases and couplers with an oxidizing agent, for example of hydrogen peroxide, let it sit, then rinse the fibers.
• the colorings which result therefrom are permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing.
• this process makes it possible to obtain a dyeing and simultaneously a lightening of the fiber which results in practice in the possibility of obtaining a final coloration lighter than the original color.
• the lightening of the fiber has the advantageous effect of generating a solid color in the case of gray hair, and in the case of naturally pigmented hair, of bringing out the color, that is to say of the make it more visible.
• direct dyes are generally sensitive to the action of oxidizing agents such as water oxygenated, which generally make them difficult to use in lightening direct dye compositions based on hydrogen peroxide and an alkalizing agent, or in oxidation dye compositions based on oxidation dyes.
• oxidizing agents such as water oxygenated
• dye compositions containing direct azo or azomethine dyes comprising at least one quaternized nitrogen atom, said compositions having to be mixed extemporaneously at basic pH with an oxidizing composition.
• These compositions make it possible to obtain colorings with homogeneous, tenacious and shiny reflections. However, they do not make it possible to dye the keratin fibers with as much power as with oxidation coloring compositions.
• patent application FR 1 353 497 which does not however relate to the dyeing of keratin fibers, discloses tetraazapentamethine compounds substituted by a benzimidazole radical and by a benzimidazolium group which are particularly suitable for dyeing fibers based on polymers or copolymers acrylic nitrile.
• - i represents a cationic heteroaromatic radical of formula (II) or (III):
• W 2 represents a heteroaromatic radical of formula (IN)
• - Z 0 represents a radical CR 2 , a nitrogen atom or a radical
• Zi represents an oxygen or sulfur atom or an NR 9 radical
• Z 2 represents a nitrogen atom or a radical CR 10 ,
• - Z 3 represents a nitrogen atom or a CR ⁇ radical
• Z 4 represents a nitrogen atom or a CR 1 radical
• Z 5 represents a nitrogen atom or a CR 13 radical
• - Z 6 represents a nitrogen atom or a radical CR 14 ,
• - Z represents an oxygen, sulfur atom or a radical - Z 8 represents a nitrogen atom or a CR 16 radical,
• - Z 9 represents a nitrogen atom or a CR ⁇ radical
• - Zi o represents a nitrogen atom or a CR 18 radical
• - Zn represents a nitrogen atom or a CR 19 radical
• - Z 12 represents a nitrogen atom or a CR 2 o radical
• Z ⁇ represents a radical CR 6 , a nitrogen atom or a radical NR 22 ,
• each of the cycles of formulas (II), (III), (IN) and (N) do not contain more than three nitrogen atoms and that two of the three nitrogen atoms can be contiguous,
• R 2 , R 6 , R 10 and R 16 represent, independently of one another, a hydrogen atom; alkyl Ci-C 4 linear or branched, unsubstituted or substituted with one to three radicals selected among the hydroxy, C ⁇ -C 2 alkoxy, (poly) -hydroxy C 2 -C 4 alkoxy, amino, (di) C ⁇ -C 2 alkylamino, carboxy or sulfonic radicals; a phenyl radical unsubstituted or substituted by one or two radicals chosen from hydroxy, C ⁇ -C 2 alkoxy, (poly) - C 2 -C 4 hydroxyalkoxy, amino, (di) C ⁇ C 2 alkylamino radicals; a carboxy radical; a sulfonylamino radical,
• R21 and R22 represent, independently of one another, an alkyl radical Ci-C 8 linear or branched, unsubstituted or substituted with one to three radicals selected from hydroxy, alkoxy C 2, (poly) hydroxyalkoxy
• R 0 , R 3 , R 8 , Rn, R12, R13, Ru, R17, Ris, R19, and R 20 represent, independently of one another, a hydrogen atom, a hydrocarbon chain Ci- C 16 linear or branched, this chain possibly being saturated or unsaturated by one to three unsaturations, this chain being unsubstituted or substituted by one to three radicals chosen from hydroxy, C 1 -C 2 alkoxy, (poly) - hydroxyalkoxy in C 2 -C 4 alkyl, amino, (di) alkylamino-C 2, carboxy, sulfonic, sulfonylamino, (poly) hydroxyalkylamino C 2 -C 4 or a halogen atom such as chlorine, fluorine or bromine; a phenyl radical unsubstituted or substituted by one to three radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxyC 2 -C 4
• R 0 , R 3 , R 8 , Ru, R12, R13, Ru, R17, Ris, R19, and R 20 do not contain a peroxide bond, nor diazo or nitroso radicals, - R 2 with Rio, R ⁇ with R 12 , R 6 with R 16 , and R ⁇ 7 with R ⁇ 8 can independently form a 5 or 6-membered carbon aromatic ring unsubstituted or substituted by one or two hydroxy radicals, amino, (di) alkyl (C1 -C 2 ) amino, alkoxy C1-C2, (poly) hydroxyalkyl C 2 -C amino,
• X is an organic or mineral anion.
• branched hydrocarbon chain within the meaning of the present application, is meant a branched hydrocarbon chain which can also form one to five carbon rings comprising from 3 to 7 members, this chain being able to comprise one to three unsaturations, that is to say one to three double bonds and / or triple bonds.
• C 2 -C 4 (poly) hydroxyalkoxy is meant a C 2 -C 4 alkoxy group substituted with 1 to 2 hydroxy groups.
• (poly) hydroxyalkyl C 2 -C 4 in the sense of the present invention means an alkylamino group substituted by 1 to 2 hydroxy groups.
• hydrocarbon chain can be interrupted by one or more oxygen, nitrogen, sulfur atoms or by an SO 2 radical, or that this chain is unsaturated means that the carbon chain can be modified by as follows:
• an organic or inorganic anion is for example chosen from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; hydrogen sulfate; a (C1-C6) alkyl sulphate such as for example a methyl sulphate or an ethyl sulphate; an acetate; a tartrate; an oxalate; an alkyl (C 6 -C) sulfonate such as methylsulfonate; unsubstituted arylsulfonate or substituted by an alkyl radical Ci-C 4 such as e.g.
• a halide such as chloride, bromide, fluoride, iodide
• a hydroxide such as a sulfate; hydrogen sulfate
• a (C1-C6) alkyl sulphate such as for example a methyl sulphate or an
• R 0 represents a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical, unsubstituted or substituted by one to three radicals chosen from hydroxy, C 1 -C 2 alkoxy, (poly) C 2 -C 4 alkoxy, amino, (di ) C1-C 2 alkylamino,
• R 0 preferably represents a hydrogen atom; alkyl Ci-C 3 linear or branched, unsubstituted or substituted with one to two radicals selected from hydroxy, alkoxy, C 1 -C 2, amino, (di) alkylamino-C2, carboxyl and sulfonic radicals; a phenyl radical unsubstituted or substituted by one to two radicals chosen from hydroxy, amino, (di) C1-C 2 alkylamino or (poly) -hydroxyalkylamino C 2 -C 4 radicals, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, pyridinyl radicals.
• R 0 represents a hydrogen atom; methyl, ethyl, propyl, butyl, 2-hydroxyethyl, 2-aminoethyl; l-carboxymethyl, 2-carboxyethyl,
• R 0 represents a hydrogen atom; a methyl, ethyl, 2-methoxyethyl radical; a phenyl radical which is unsubstituted or substituted by an amino, (di) methylamino, (di) (2-hydroxyethyl) amino radical, an optionally cationic heteroaryl radical chosen from imidazolyl and pyridinyl radicals.
• R 2 , R 6 , R 10 and R ⁇ 6 preferably represent a hydrogen atom, a phenyl radical, a C 1 -C 4 alkyl radical unsubstituted or substituted by one or two radicals chosen from hydroxy, amino, (di ) C 1 -C 2 alkylamino, carboxy.
• R2, R 6 , Rio and R 16 preferably represent a hydrogen atom, a methyl, phenyl, 2-hydroxymethyl radical, a carboxy, a phenyl radical.
• Ri, R 4 , R 5 , R 7 , R 9 , R ⁇ 5 , R 21 and R22 preferably represent a C 1 -C 4 alkyl radical unsubstituted or substituted by one or two radicals chosen from hydroxy, C1 alkoxy radicals -C2, amino, (di) C1-C2 alkylamino, carboxy, sulfonic.
• R l 5 R 4 , R 5 , R 7 , R 9 , R 15 , R 2 ⁇ and R 22 preferably represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2- radical. carboxyethyl, 2-sulfonylethyl.
• R 3 , R 8j R ⁇ , R 12 , R13, R 14 , R 17 , R 18 , R ⁇ 9 , and R 20 represent, preferably and independently of one another, a hydrogen atom; a linear or branched C ⁇ -C 4 alkyl radical, unsubstituted or substituted by one to two radicals chosen from hydroxy, C1-C2 alkoxy, (poly) -hydroxy C 2 -C 4 alkoxy, amino, (di ) C 1 -C 2 alkylamino, carboxy or sulfonic; phenyl unsubstituted or substituted with one to two radicals selected from hydroxy, alkoxy C 1 -C 2 alkyl, (poly) hydroxyalkoxy, C 2 -C 4 alkyl, amino, (di) alkylamino-C 2, carboxy, sulfonic or a halogen atom such as chlorine, fluorine, or bromine; a sulfonylamin
• R3, R 8; R ⁇ , R 12, Ri3, R ⁇ , R17, Ris, R19, and R20 represent a hydrogen atom, an alkyl radical Ci-C 4 unsubstituted or substituted with one to two radicals selected from hydroxy, alkoxy in Ci-C 2 ; an amino radical; a C1-C2 alkyl (di) alkylamino radical; a carboxy radical; a C2-C 4 (poly) -hydroxyalkylamino radical.
• R 3 R 8j R ⁇ , Ri2, R13, R14, R17, Ris, R19, and R20 independently of one another hydrogen, methyl, 2-hydroxymethyl, a carboxy, a methoxy, ethoxy, 2-hydroxyethyloxy radical, an amino, methylamino, dimethylamino, 2-hy droxy ethylamino radical.
• the compounds of formula (I) preferably used are those for which in formula (I) i is a 2-benzimidazolium radical and 2 is a 2-benzimidazole radical. Even more preferably, these are the following compounds:
• a second object and of the present application consists of a composition for dyeing keratin fibers, and in particular human keratin fibers and more particularly the hair comprising, in a medium suitable for dyeing, at least one compound of formula (I) , as a direct dye.
• the compounds of formula (I) are present in the composition according to the present invention in a concentration by weight ranging from 0.001 to 5%, preferably ranging from 0.05 to 2% relative to the total weight of the composition.
• the composition according to the present invention also comprises at least one direct dye different from those of formula (I) according to the invention and chosen in particular from the group formed by neutral nitrous direct dyes, acidic or cationic, dyes azo acid neutral or cationic direct, quinone direct dyes and in particular neutral, acid or cationic anthraquinone dyes, azine direct dyes, methine direct dyes, triarylmethane direct dyes, indoamine dyes and natural direct dyes.
• the additional direct dye (s) preferably represent from 0.001 to 20% by weight approximately of the total weight of the composition and even more preferably from 0.005 to 10% by weight approximately.
• the composition of the invention may also comprise an oxidizing agent.
• This oxidizing agent can be any agent oxidant conventionally used for coloring or bleaching keratin fibers.
• the oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and enzymes among which the oxides can be mentioned. 2 electron reductases such as uricases, peroxidases and 4 electron oxidoreductases such as laccases.
• the use of hydrogen peroxide is particularly preferred as an oxidizing agent.
• the composition according to the invention can also comprise an oxidation base.
• This oxidation base can be chosen from the oxidation bases conventionally used in oxidation dyeing, for example paraphenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
• composition according to the invention may also contain one or more couplers conventionally used for dyeing keratin fibers.
• couplers conventionally used for dyeing keratin fibers.
• couplers mention may in particular be made of metaphenylenediamines, metaaminophenols, metadiphenols, naphthalene couplers and heterocyclic couplers.
• the coupler (s) are generally present in an amount ranging from 0.001 to 10% by weight approximately of the total weight of the dye composition and more preferably from 0.005 to 6%.
• the oxidation base (s) are present in an amount preferably ranging from 0.001 to 10% by weight approximately of the total weight of the dye composition, and more preferably from 0.005 to 6%.
• the addition salts with an acid which can be used in the context of the dye compositions of the invention for the oxidation bases and the couplers are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
• the medium suitable for dyeing also called support • dyeing generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water.
• organic solvent mention may, for example, be made of lower C 1 -C 4 alkanols such as ethanol and isopropanol, polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
• lower C 1 -C 4 alkanols such as ethanol and isopropanol
• polyols and polyol ethers such as 2-butoxyethanol
• propylene glycol propylene glycol monomethyl ether
• monoethyl ether monoethyl ether
• diethylene glycol monomethyl ether diethylene glycol monomethyl ether
• aromatic alcohols such as benzyl alcohol or phenoxyethanol
• the organic solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
• the dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular anionic, cationic, nonionic and amphoteric associative polymers, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
• the adjuvants mentioned above are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the composition.
• the pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 1 1 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.
• acidifying agents there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
• mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.
• basifying agents there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and tri-ethanolamine s as well as their derivatives, sodium and potassium hydroxides and the compounds of formula (III) below:
• W is a propylene residue optionally substituted with a hydroxyl group or an alkyl radical Ci-C 4, R a, Rb, Rc and Rd, identical or different, represent a hydrogen atom, an alkyl radical C ⁇ -C or C 1 -C 4 hydroxyalkyl.
• 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.
• a third object of the present invention consists in a direct dyeing process which comprises the application of a dye composition comprising at least one dye of formula (I) as defined above on keratin fibers, in particular human keratin fibers and more especially the hair for a sufficient time to develop the desired coloring. The fibers are then rinsed and dried.
• the application to the keratin fibers of the composition containing the dye of formula (I) can be implemented in the presence of an oxidizing agent, which causes discoloration of the fiber
• This oxidizing agent can be added to the composition containing the dye of formula (I) at the time of use or directly on the keratin fiber.
• the invention also relates to an oxidation dyeing process which comprises applying to the fibers a dye composition which comprises at least one dye of formula
• the oxidation base, the coupler and the oxidizing agent are as defined above.
• the color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition according to the invention just at the time of use or it can be used from an oxidizing composition containing it , it is then applied to the fibers simultaneously or sequentially to the dye composition.
• the dye composition is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration.
• the mixture obtained is then applied to the keratin fibers. After a pause time of approximately 3 to 50 minutes, preferably approximately 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.
• the oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
• the pH of the oxidizing composition containing the oxidizing agent is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11 It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.
• composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and in particular human hair.
• the present invention further relates to a process for bleaching direct dyes, which are the subject of the invention and which have just been described.
• this bleaching process can be applied to keratin fibers previously dyed in accordance with the dyeing processes which have just been described.
• One of the advantages of this process is that the natural color of the fibers before dyeing with the composition according to the invention is retained, only the color provided by the direct dye is eliminated.
• This process also has the advantage of being quick and easy to implement.
• the method consists in applying to the compound of formula (I) and (F) a bleaching composition comprising at least one reducing agent chosen from reducing agents comprising sulfur.
• the process in the case where the process is applied to keratin fibers, it consists in implementing the following steps: a) a bleaching composition comprising, in a medium, is applied to the fibers previously treated with a dye composition suitable, at least one reducing agent chosen from reducing agents comprising sulfur; b) it is allowed to pause for a sufficient time to have discoloration; c) the fibers are optionally rinsed; d) the fibers are washed, rinsed and then dried.
• the reducing agents comprising sulfur are chosen from compounds having at least one thiol, sulphide or sulphite function.
• thioglycolic acid thiolactic acid, their alkali or alkaline earth metal salts (such as sodium, potassium, calcium) and their esters; ⁇ -mercaptoethanol, cysteine, cysteamine and their derivatives; homocysteine and one of its salts; mercaptoaldehydes; penicillamine; glutathione.
• alkali or alkaline earth metal salts such as sodium, potassium, calcium
• esters such as sodium, potassium, calcium
• ⁇ -mercaptoethanol cysteine, cysteamine and their derivatives
• homocysteine and one of its salts mercaptoaldehydes
• penicillamine glutathione
• sulphites which can be used as reducing agents, among which also include the bisulphites, the hydrosulphites, the alkali metal, alkaline earth metal or ammonium salts, as well as their mixtures, are suitable. More particularly, cm can cite sodium sulfite, sudium metasulfite
• cystine can in particular be cited.
• the content of reducing agent in the composition is advantageously between 0.01 and 10% by weight of the dye bleaching composition, preferably between 0, 1 and 5
• the medium of the composition conventionally comprises water or an organic solvent. What has been indicated previously with respect to the middle of the dye composition remains valid and may be referred to.
• composition can likewise comprise conventional adjuvants such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or their mixtures, anionic, cationic, nonionic, amphoteric polymers, zwitterionics or their mixtures, mineral or organic thickening agents, and in particular anionic, cationic, nonionic and amphoteric associative polymers, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.
• adjuvants such as anionic, cationic, non-ionic, amphoteric, zwitterionic surfactants or their mixtures, anionic, cationic, nonionic, amphoteric polymers, zwitterionics or their mixtures, mineral or organic thickening agents, and in particular anionic, cationic, non
• the adjuvants mentioned above are generally present in an amount for each of them of between 0.01 and 20% by weight relative to the weight of the bleaching composition.
• these optional adjuvants in such a way that "the advantageous properties intrinsically attached to the use of the bleaching composition are not, or not substantially, altered by the one or more planned additions.
• the pH of the bleaching composition is generally between 6 and 10, advantageously between 7 and 9. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in the field, lists of which have been given previously. , or even using conventional buffer systems.
• the bleaching composition can be applied equally to dry or wet hair.
• the temperature at which the bleaching process is implemented is between 15 and 50 ° C, preferably close to room temperature.
• the pause time of the composition is generally between 1 and 30 minutes, more particularly between 2 and 20 minutes. It should be noted that this range is given for information only. Indeed, this can be determined without difficulty by those skilled in the art, the discoloration of the hair can be observed visually, because the phenomenon is visible. Generally, the higher the content of reducing agent and / or the higher the temperature, the less the duration of there is a long break to bleach the dye or the hair previously dyed with the dyes according to the invention.
• the present invention also relates to the tetraazapentamethine compounds of formula (I 1 ):
• W 2 represents a heteroaromatic radical of formula (IV) or
• Z'o represents a radical CR ' 2 , a nitrogen atom or a radical NR'21,
• - Z 'i represents an oxygen atom or a radical NR' 9
• - Z'2 represents a nitrogen atom or a radical CR '10
• - Z ' 3 represents a nitrogen atom or a radical CR' ⁇
• - Z ' 4 represents a nitrogen atom or a radical CR' 1 2,
• Z ' 5 represents a nitrogen atom or a radical CR' 13 ,
• Z ' 6 represents a nitrogen atom or a radical CR' 14;
• Z ' 7 represents an oxygen atom or an NR' 15 radical,
• - Z ' 8 represents a nitrogen atom or a radical CR' 16 ,
• - Z ' 9 represents a nitrogen atom or a radical CR' 1 ,
• Z 'io represents a nitrogen atom or a radical CR' 18 ,
• - Z ' ⁇ represents a nitrogen atom or a CR' 19 radical
• - Z '12 represents a nitrogen atom or a CR'20 radical
• Z '13 represents a radical CR' 6 , a nitrogen atom or a radical NR'22,
• each of the cycles of formulas (II '), (IH'), (IV) and (V) do not contain more than three nitrogen atoms, and that two of the three nitrogen atoms can be contiguous,
• R'2, R ' 6 , R'10 and R' 16 represent, independently of one another, a hydrogen atom; a linear or branched C ⁇ -C 4 alkyl radical, unsubstituted or substituted by one to three radicals chosen from hydroxy, C1-C2 alkoxy, (poly) -hydroxy C 2 -C 4 alkoxy, amino, (di) C 1 -C 2 alkylamino, carboxy or sulfonic; an unsubstituted phenyl radical or substituted by one or two radicals selected from hydroxy, alkoxy C 2, (poly) - hydroxyalkoxy, C 2 -C 4 alkyl, amino, (di) alkylamino, C 1 -C 2 alkyl; a carboxy radical; a sulfonylamino radical,
• R 'i, R' 4 , R ' 5 , R' 7 ,, R ' 9 , R' 15 , R'21, and R'22 represent, independently of each other, a C ⁇ - alkyl radical C 8 linear or branched, unsubstituted or substituted by one to three radicals chosen from hydroxy, C ⁇ -C 2 alkoxy, (poly) hydroxy C 2 -C 4 alkoxy, amino, (di) alkylamino Ci-C 2 , carboxy or sulfonic;
• R'o, R'3, R's, R '11, R' 12, R 'n, R' i4, R '17, R'is, R' 19, and R'20 independently represent one of the other, a hydrogen atom, a linear or branched C ⁇ -C 16 hydrocarbon chain, this chain possibly being saturated or unsaturated by one to three unsaturations, this chain being unsubstituted or substituted by one to three radicals chosen from hydroxy, C1-C2 alkoxy, (poly) - C2-C 4 hydroxyalkoxy, amino, (di) C1-C 2 alkylamino, carboxy, sulfonic, sulfonylamino, (poly) -hydroxy C2-C 4 alkylamino or a halogen atom such as chlorine, fluorine or bromine; a phenyl radical unsubstituted or substituted by one to three radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxyC
• R - R '2 with R io, R' ⁇ R '12, R' 6 R '16 and R' 17 to R '18 can form, independently of each other a carbonaceous aromatic 5- or 6-membered unsubstituted or substituted by one or two hydroxy, amino, (di) alkyl (Ci-C 2 ) amino, alkoxyen C 1 -C 2 , (poly) hydroxyalkyl (C 2 -C 4 ) amino radicals, provided that W ' i and W'2 do not simultaneously represent the same bicyclic system,
• R ' 0 , R'3, R' ⁇ , R '11, R' 12, R ' ⁇ , R' u, R '17, R' i8, R '19, and R'20 do not contain no peroxide bond, no diazo or nitroso radicals,
• - - X is an organic or mineral anion.
• R ' 0 preferably represents a hydrogen atom; a linear or branched C ⁇ -C 6 alkyl radical, unsubstituted or substituted by one to three radicals chosen from hydroxy, C1-C2 alkoxy, (poly) hydroxy C 2 -C 4 alkoxy, amino, (di) alkylamino-C 2, (poly) hydroxyalkylamino C 2 -C 4, carboxy or sulpho; a phenyl radical, unsubstituted or substituted by one to three radicals chosen from hydroxy, C 1 -C 2 alkoxy, (poly) hydroxy C 2 -C 4 alkoxy, amino, (di) C 1-6 alkylamino radicals
• C 2 carboxy, sulfonic or a halogen atom such as chlorine, fluorine or bromine; an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, triazolyl, pyridinyl, pyrimidinyletriazinyl, pyrazinyl, pyridazinyl radicals.
• R'o preferably represents a hydrogen atom; a linear or branched C ⁇ -C 3 alkyl radical, unsubstituted or substituted by one to two radicals chosen from hydroxy, C 1 -C 2 alkoxy, amino, (di) C1-C2 alkylamino, carboxy or sulfonic; a phenyl radical, unsubstituted or substituted by one to two radicals chosen from hydroxy, amino, (di) C1-C 2 alkylamino or (poly) - hydroxy-C 2 -C 4 alkyl radicals, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, pyridinyl radicals.
• R 'o represents a hydrogen atom; methyl, ethyl, propyl, butyl, 2-hydroxy ethyl, 2-aminoethyl; 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl, 2-methoxyethyl; a phenyl radical, unsubstituted or substituted by one to two radicals chosen from amino, (di) C 1 -C 2 alkylamino, (poly) -hydroxyalkylamino C 2 -C 4 radicals, an optionally cationic heteroaryl radical chosen from pyrazolyl radicals , pyrrolyle, imidazolyle, pyridinyle.
• R'o represents a hydrogen atom; a methyl, ethyl, 2-methoxyethyl radical; a phenyl radical unsubstituted or substituted by an amino, (di) methylamino, (di) (2-hydroxyethyl) amino radical, an optionally cationic heteroaryl radical chosen from pyrazolyl, pyrrolyl, imidazolyl, pyridinyl radicals.
• R '2, R' 6, R io and R 16 preferably represent a hydrogen atom, an alkyl radical Ci-C 4 unsubstituted or substituted with one to two radicals selected from hydroxy, amino, (di ) C1-C2 alkylamino, carboxy, a phenyl radical.
• R'2, R ' 6 preferably represent a hydrogen atom, an alkyl radical Ci-C 4 unsubstituted or substituted with one to two radicals selected from hydroxy, amino, (di ) C1-C2 alkylamino, carboxy, a phenyl radical.
• R '10 and R' 16 preferably represent a hydrogen atom, a methyl, phenyl, 2-hydroxymethyl radical, a carboxy.
• R 'i, R' 4, R '5, R' 7, R '9, R' is, R'21 and R 22 preferably represent an alkyl radical C ⁇ -C 4 unsubstituted or substituted with one to two radicals chosen from hydroxy, C 1 -C 2 alkoxy, amino, (di) alkylamino C 1 -C 2 , carboxy, sulfonic radicals.
• R 'i, R' 4 , R's, R'7, R'9, R '15, R'21 and R'22 preferably represent a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, radical. 2- carboxyethyl, 2-sulfonylethyl.
• R ' 3 , R' 8 , R ' ⁇ , R' 12, R 'is, R' i4, R '17, R' is, R 'i9, and R' 20 represent, preferably and independently one of l other, a hydrogen atom; alkyl C ⁇ -C 4 linear or branched, unsubstituted or substituted with one to two radicals selected from hydroxy, alkoxy C 1 -C 2 alkyl, (poly) hydroxyalkoxy, C2-C4, amino, (di ) C 1 -C 2 alkylamino, carboxy or sulfonic; a phenyl radical, unsubstituted or substituted by one or two radicals chosen from hydroxy, C ⁇ -C 2 alkoxy, (poly) -hydroxyalkoxy radicals
• C 2 -C 4 amino, (di) C 1 -C 2 alkylamino, carboxy, sulfonic or a halogen atom such as chlorine, fluorine or bromine; a sulfonylamino radical; a C2-C 4 (poly) -hydroxyalkylamino radical.
• R ' 3 , R' s, R '11, R' 12, R '13, R' i4, R '17, R' i8, R ' 1 9, and R' 2 0 represent an atom of ' hydrogen, Ci-C 4 alkyl, unsubstituted or substituted with one to two radicals selected from hydroxy, alkoxy C 1 -C 2 radical; an amino radical; a C1-C2 (di) alkylamino radical; a carboxy radical; a (poly) -hydroxy C 2 -C 4 alkylamino radical.
• R'3, R ' 8j represent an atom of ' hydrogen, Ci-C 4 alkyl, unsubstituted or substituted with one to two radicals selected from hydroxy, alkoxy C 1 -C 2 radical; an amino radical; a C1-C2 (di) alkylamino radical; a carboxy radical; a (poly) -hydroxy C 2 -C 4 alkylamino
• R ' ⁇ , R' 12, R '13, R' i4, R '17, R' is, R '19, and R' 2 o independently of one another represent a hydrogen atom, a radical methyl, 2-hydroxymethyl, carboxy, methoxy, ethoxy, 2-hydroxyethyloxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino radical.
• the compounds of formula F are chosen from the family defined by the compounds for which W'i is a 2-pyridinium radical and W ' 2 is a 2-pyridine radical. Even more preferably, these are the following compounds: - 2- [5- (N-methyl-2-pyridinylidene) - l-formazano] chloride -
• the compounds of formula F are chosen from the family defined by the compounds for which W'i is a 4-pyridinium radical and W ' 2 is a 4-pyridine radical. Even more preferably, these are the following compounds:
• the compounds of formula F are chosen from the family defined by the compounds for which W'i is a 2-imidazolium radical and W ' 2 is a 2-imidazole radical. Even more preferably, these are the following compounds:
• the compounds of formula F are chosen from the family defined by the compounds for which W'i is a 5-pyrazolium radical and W ' 2 is a 5-pyrazole radical. Even more preferably, these are the following compounds:
• the compounds of formula F are chosen from the family defined by the compounds for which W'i is a 2-benzimidazolium radical and W ' 2 is a 2-pyridine radical. Even more preferably, these are the following compounds:
• the compounds of formula I ' are chosen from the family defined by the compounds for which W'i is a 2-benzimidazolium radical and W' 2 is a 4-pyridine radical. Even more preferably, these are the following compounds:
• the compounds of formula F are chosen from the family defined by the compounds for which W'i is a 2-imidazolium radical and W ' 2 is a 2-pyridine radical. Even more preferably, these are the following compounds:
• the compounds of formula F are chosen from the family defined by the compounds for which W'i is a 2-imidazolium radical and W ' 2 is a 4-pyridine radical. Even more preferably, these are the following compounds: - 2- [5- (N-methyl-4-pyridinylidene) - l -formazano] chloride -
• the compounds and families of new compounds presented in the above lists can be used as direct dyes in the dye compositions according to the invention.
• the present invention also relates to a process for the preparation of the compound of formula (F) in which at least two equivalents of at least one hydrazone chosen from hydrazones of formula A and hydrazones of formula B are reacted:
• Y being an organic or mineral anion
• x being an integer ranging from 1 to 3
• Z ⁇ , Z ⁇ 8 , Z 1 , Z20, R26, R27 respectively have the same meanings as Z ' 9 , Z'io, Z' ⁇ , Z'i2, R's, R * 7 of the formula V, Y' being an anion organic or mineral, x 'being an integer ranging from 1 to 3, with an equivalent of an aldehyde of formula R 2 3CHO, R23 having the same meaning as R'o of formula I'. It is thus possible to react two equivalents of the same hydrazone or of two different hydrazones.
• the aldehyde of formula R 2 3CHO is generated in the reaction medium from an aldehyde precursor of formula R'2 3 CH 2 ⁇ H in the presence of an oxidizing system, R'23 then the same meaning as R'o of formula I '.
• This oxidizing system can be a chemical oxidant or a biocatalytic oxidant such as an enzyme.
• the process for preparing the compound of formula (F) according to the present invention can be implemented in the presence of an aldehyde precursor of formula R 2 3CH 2 OH and at least one enzyme capable of generating an aldehyde from the aldehyde precursor of formula R ' 2 3CH 2 ⁇ H.
• the process for the synthesis of the compounds of formula (I) by the enzymatic route defined above is carried out by reacting at least two equivalents of at least one hydrazone chosen from the hydrazones of formula A and the hydrazones of formula B in which Z ⁇ 4 , Z ⁇ 5 , Z ⁇ 6 ,
• R 25 respectively have the same meanings as Z 7 , Z 8 , Z 1 3, R5 of the formula IN,
• Y being an organic or mineral anion
• x being an integer ranging from 1 to 3
• Z ⁇ , Z ⁇ 8 , Z ⁇ 9 , Z20, R 2 ⁇ , R27 respectively have the same meanings as Z, Z10, Z ⁇ , Z12, Rs, R7 of the formula N,
• Y ' being an organic or mineral anion, x' being an integer ranging from 1 to 3, with an equivalent of an aldehyde of formula R23CHO, R 2 3 having the same meaning as Ro of formula I.
• the present invention also relates to such a method.
• the reaction is carried out with or without an oxidizing system, with or without a cofactor for the enzyme, with or without a cofactor regeneration system.
• an oxidizing system with or without a cofactor for the enzyme, with or without a cofactor regeneration system.
• the term "without oxidizing system” means that no oxidizing system other than atmospheric oxygen is used.
• the reaction is carried out in an aerobic medium at a pH between 3 and 11 and at a temperature between 6 ° C and 80 ° C.
• the aldehyde precursor which can be used to prepare the compound of formula (F) or the compound of formula (I) can be chosen from primary alcohols, sarcosine, 4-hydroxymandelate, ⁇ 6- methyl-lysine, dimethylglycine, methylglutamate, 2-oxo-acids for example 2-oxo-acid pyruvate, benzoylformate, phenylpyruvate, threonine.
• it will be chosen from primary alcohols.
• the enzymes capable of generating an aldehyde from this aldehyde precursor can in particular be chosen from alcohol dehydrogenases EC 1.1.1.1, alcohol dehydrogenases EC
• N-methyl L amino acid oxidase EC 1.5.3.2 N-methyl-L-amino acid
• trimethylamine dehydrogenase EC 1.5 N-methyl L amino acid oxidase EC 1.5.3.2 (N-methyl-L-amino acid), trimethylamine dehydrogenase EC 1.5.
• Examples of useful enzymes that may be mentioned in particular are the genera Plectranthus, Pinus, Gastropod, Manduca, Pichia, Candida, Pleurotus, Pseudomonas, and even more particularly the following species: Plectranthus colleoides, Pinus strobus which is a plant origin, Gastropod mollusc, Manduca sexta which are of animal origin, Pichia pastoris and Candida boidinii which are yeasts, Pleurotus pulmonarius which is a fungus, and Pseudomonas pseudoalcaligenes which is a bacterium.
• the choice of enzyme depends on the nature of the aldehyde precursor. For example, when the aldehyde precursor is an alcohol, then the enzyme is chosen from enzymes capable of generating an aldehyde from this alcohol. When the aldehyde precursor is methylglutamate, then the enzyme is a methylglutamate dehydrogenase.
• the aldehyde precursor is a primary alcohol and the enzyme is an enzyme capable of generating the aldehyde from an alcohol.
• the enzyme capable of generating the aldehyde is chosen from alcohol oxidases, alcohol dehydrogenases, methanol dehydrogenases, methanol oxidases.
• the primary alcohol is benzyl alcohol, 4-terbutyl benzyl alcohol, 3-hydroxy-4-methoxybenzyl alcohol, veratryl alcohol, 4-methoxybenzyl alcohol, cinnamic alcohol, 2,4 hexadien- 1 -ol, aryl alcohol oxidases or aromatic alcohol dehydrogenases can be used as the aldehyde precursor.
• dehydrogenase enzymes it is essential to include the cofactor (s) necessary for their activity, more precisely NAD + or NADP + or other molecules capable of acting as an electron acceptor.
• cofactor regeneration system can be used for reaction or economic reasons. This regeneration system can be enzymatic, chemical or electrochemical.
• the most diverse oxidants can be used for the implementation of this process: hydrogen peroxide, organic peracids such as peracetic acid, persalts such as permanganate, perborate, persulfates, chromates or dichromates, hypochlorites , hypobromites, ferricyanides, peroxides such as manganese or lead bioxides.
• hydrogen peroxide will be used.
• the substrate concentration of the enzyme can be between 0.001M and 6M, preferably between 0.1M and 4M.
• the reaction can be carried out between pH 3 and pH 11 preferably between pH 5 and pH 9.5.
• the temperature for the reaction can be between 10 ° C and 80 ° C, preferably between 20 ° C and 65 ° C.
• the concentration of hydrazone in the reaction medium is between 0.01M and 3M, preferably between 0.1M and 1M.
• the cofactor content for the said enzymes can be between 0.01 mM and 1 M, preferably 0.1 lmM and 10 mM.
• the reagents the hydrazone (s), the enzyme (s), the substrate for said enzyme, and / or the cofactor for said enzyme , and / or the oxidant and / or the regeneration system of the cofactor are mixed, the pH and the temperature are adjusted.
• the present invention also relates to a process for the preparation of the compound of formula (F) in which a compound of formula (F I) or (F2) is reacted
• the compounds of formula (FI) or (F2) can be obtained by reaction of a compound of formula R n 2 3C (OR 24 ) 3 and of a hydrazone of formula (A) or (B) in the presence or not of a protic solvent whose boiling point varies between 66 ° C and 180 ° C.
• R ⁇ 2 3 has the same meaning as R'o of the formula (F) and R 2 4 represents a radical chosen from methyl and ethyl groups.
• the reaction is carried out in the presence of triethylorthoformate and trimethylorthoacetate at a temperature between 0 ° C and 150 ° C for a period between 30 minutes and 12 hours.
• the protic solvent is chosen from H 2 O, ethanol, and methanol.
• the compounds mentioned in formula (F) can be synthesized in reacting at least one hydrazone as defined in formulas (A) and (B) with one or more enzymes of the type: alcohol oxidase, alcohol dehydrogenase, oxidoreductase, transferase, and / or lyase, and the substrate (s) of formula R'23CH 2 ⁇ H for said enzyme (s) with or without oxidant, with or without cofactor for the enzyme, with or without regeneration system of said cofactor.
• the reaction is carried out between pH 3 and pH 11 in an aerobic medium at a temperature between 10 ° C and 80 ° C.
• Example n ° l Detection in ESI + M + 329 lambda max 578nm
• Example n ° 2 Detection ESI + M + 315 lambda max 556nm
• Example n ° 3 Detection ESI + M + 329 lambda max 564nm
• Example n ° 4 Detection ESI + M + 391 lambda max 576nm
• Example n ° 5 Detection ESI + M + 255 lambda max 569nm
• Example n ° 6 Detection in ESI + M + 275 lambda max 528nm
• Example n ° 7 Detection ESI + M + 261 lambda max 534nm
• Example n ° 8 Detection ESI + M + 285 lambda max 572nm
• a color appears between 24 hours and 72 hours at room temperature.
• Example No. 9 lambda max 568 nm
• Example No. 10 lambda max 630 nm
• Example No. 11 lambda max 556 nm
• the reaction is carried out between pH 3 and pH 11 preferably between pH 5 and pH 9.5 in an aerobic medium at a temperature between 10 ° C and 80 ° C preferably between 20 ° C and 65 ° C.
• the oxidoreductases used will be chosen from the following enzymes from group EC 1.10.3 by way of example catechol oxidase EC 1.10.3.1, Laccase EC 1.10.3.2, L ascorbate oxidase EC 1.10.3.3 and aminophenol oxidase EC 1.10.3.4.
• the compound of formula (A ') or (B') is the substrate for the said enzyme (s).
• a mediator can be introduced into the reaction mixture to improve the reaction rate. Said mediator serves as an intermediate reagent between the enzyme and the compound of formula (A ') or (B') or the compound of formula (A) or (B).
• usable mediators mention may be made of
• the concentration of the reaction medium in compound of formula (A) or (B) is between 0.01M and 3M preferably between 0.1M and 1M.
• the concentration of reaction medium in compound of formula (A ') or (B') is between 0.01M and 3M preferably between 0.1M and 1M.
• reagents: the compound of formula (A) or (B) and the compound of formula (A ') or (B'), the enzyme (s), and or the mediator for said enzyme, and or the oxidant are mixed , the pH and the temperature are adjusted.
• the hydrazone of formula (A) or (B) used for the synthesis is reacted in the presence of an equivalent of a compound of formula R u 2 3C (OR2 4 ) 3 and optionally a protic solvent whose boiling point varies between 66 ° C and 180 ° C at a temperature between 30 ° C and 150 ° C with stirring.
• the hydrazone of formula (A) or (B) is reacted in the presence of trimethylorthoformate or triethylorthoacetate and optionally a solvent preferably chosen from methanol and ethanol, at a temperature between 100 ° C. and 150 ° C, for a period between 30 and 60 minutes.
• the oxidizing agent is chosen from O 2 , Na 2 O, K 3 Fe (CN) 6 , MnO 2 , H 2 O 2 , Ag 2 O, AgO, NiO 2 , NaBO 3 , Na 2 S 2 O 8 , CH 3 CO 3 H, C 6 H 5 CO 3 H, (NH 4 ) 2 Ce (NO 3 ) 6 , PbO 2 , Pb (OCOCH 3 ) 4 , SeO, CrO 3. 2 C 5 H 4 N.
• the preferred oxidants will be chosen from K 3 Fe (CN) 6 , MnO 2 , H 2 O 2 , Pb (OCOCH 3 ) 4 .
• the preferential oxidizing agents will be chosen from
• the reaction is preferably carried out at a temperature between 0 ° C and 80 ° C in a preferably polar solvent at a pH between 5 and 9.5
• the hydrazone 1 (4.28 g, 0.01998 mol) was stirred at 130 ° C. for 12 hours in the presence of triethylorthoformate (50 ml, 0.30 mol).
• the reaction medium was cooled and the product was precipitated from diisopropyl ether. The precipitate was filtered under vacuum and then stored under argon. Quantitative yield.
• composition was applied on the one hand to locks of natural gray hair containing 90% white hairs, on the other hand to locks of permanent gray hair containing 90% white hairs, for 30 minutes at room temperature (20 ° C.) .
• the locks were rinsed, shampooed, then rinsed and dried. They were dyed in a very chromatic blue-violet shade.
• Example 1 An aqueous dye solution of Example 1 according to the invention (at 0.5% by weight), at pH 7 (phosphate buffer) is applied to a lock of natural gray hair containing 90% white hairs (0.5 g). 0.1 M potassium) and leave to stand for 30 minutes at room temperature
• the wick is then rinsed, shampooed and then dried. It was dyed in a very chromatic blue-violet shade.
• the wick is then rinsed, shampooed and then dried.
• the lock obtained is discolored.
• a lock of gray color is obtained, ie the initial color of the hair before the coloring treatment (step a).

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