FR3117823A1 - Hair coloring process using specific resorcinol derivatives, associated compositions and new compounds - Google Patents

Abstract

The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step i) of applying to said keratin fibers a composition comprising or more compounds chosen from the compounds of formula (I) as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates:(I) The present invention also relates to a cosmetic composition comprising compounds according to the invention, and a multi-compartment device suitable for implementing the method. The invention finally relates to new particular compounds, useful as couplers in oxidation coloring.

Description

Hair coloring process using specific resorcinol derivatives, associated compositions and new compounds

The present invention relates to a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising a step of applying to said fibers a composition comprising one or more particular compounds derived from resorcinol as defined below. After.

A subject of the invention is also a cosmetic dye composition comprising one or more such compounds and one or more oxidation bases.

The present invention also relates to one or more specific compounds derived from resorcinol, which are useful for the oxidation coloring of keratin fibers.

It is known to dye keratin fibres, and in particular human hair, with dye compositions containing precursors of oxidation dyes, generally called oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para- -aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise to colored compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diaminobenzenes, meta-aminophenols, meta- diphenols and certain heterocyclic compounds such as indole compounds.

The variety of molecules involved in oxidation bases and couplers allows a rich palette of colors to be obtained.

The so-called "permanent" coloration obtained by virtue of these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be toxicologically harmless, it must make it possible to obtain shades in the desired intensity and have good resistance to external agents such as light, bad weather, washing, hair treatments in temporary or permanent form, perspiration and friction.

The dyes must also make it possible to cover the white hair and be the least selective possible, that is to say make it possible to obtain the smallest possible differences in coloring throughout the same lock of keratin fiber, which is generally differently sensitized (that is to say damaged) between its tip and its root.

We know in particular the use as couplers of compounds belonging to the family of meta-diphenols such as resorcinol and its alkylated derivatives such as for example 2-methyl-resorcinol.

Nevertheless, the coloring results obtained with these couplers are not always completely satisfactory, in particular in terms of increase in coloring, selectivity, chromaticity, intensity and/or persistence, in particular with successive shampoos, or resistance to light or perspiration.

In addition, demand is growing for coloring products using compounds of natural origin or occurrence, while maintaining an excellent level of dyeing performance.

There is therefore a real need to have oxidation couplers, in particular of natural origin or occurrence, which make it possible to dye the keratin fibers in an intense, tenacious, not very selective, chromatic way, with a good rise in color, and capable of leading to colorations that are resistant to the various attacks that the fibers can undergo such as bad weather, washing and perspiration.

These objects are achieved with the present invention, the subject of which is in particular a process for dyeing keratin fibres, in particular human keratin fibers such as the hair, comprising at least one step i) of applying to said keratin fibers a composition comprising one or more compounds chosen from the compounds of formula (I) below, as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates:

formula (I) in which:
-R₁represents a hydrogen atom, a hydroxy group, or a C-linear alkoxy group₁-VS₅optionally substituted by one or more groups chosen from a hydroxy group and an amino group;
-R₂represents a hydrogen atom, a hydroxy group, a C (hydroxy)alkoxy group₁-VS₃, or a linear C-alkyl group₁-VS₅optionally substituted by one or more groups chosen from a hydroxy group and an amino group;
-R₃represents a hydrogen atom, a hydroxy group, a C (hydroxy)alkyl group₁-VS₅, a C alkoxy group₁-VS₃, an alkoxy group (C₁-VS₃)methyloxy, a C (hydroxy)alkoxycarbonyl group₁-VS₃, a (di)((hydroxy)alkyl C₁-VS₅)aminocarbonyl, a hydroxycarbonyl (-COOH) group, an -SO group₃H, or a -PO group₃H;
-R₄represents a hydrogen atom or a C (hydroxy)alkyl group₁-VS₆linear or branched;
-R₅and R'₅represent, independently of one another, a hydrogen atom, an amino group, a hydroxy group, a hydroxycarbonyl group (-COOH), a linear C-alkyl group₁-VS₃optionally substituted by a hydroxycarbonyl radical (-COOH) or an aromatic group, such as in particular a phenyl radical optionally substituted by a hydroxy group;
-R₆and R'₆represent, independently of each other, a hydrogen atom or a linear C-alkyl group₁-VS₃.

The compounds defined above lead to a wide color palette in oxidation coloration. They make it possible to obtain colorations with very varied shades. They also have good solubility in conventional staining supports, in particular aqueous media. These compounds can be used as couplers in oxidation coloring compositions, replacing resorcinol and 2-methylresorcinol, and make it possible to obtain shades close to those obtained with resorcinol and 2-methylresorcinol.

In addition, these compounds make it possible to dye keratinous fibers in a satisfactory manner, in particular by leading to powerful, tenacious, chromatic, not very selective colorations, with a good rise in color.

The compounds according to the invention thus make it possible to lead to colorations which are resistant to the various attacks which the keratin fibers may undergo, such as bad weather, light, washing and/or perspiration.

The present invention also relates to a cosmetic composition comprising:
- one or more compounds chosen from the compounds of formula (I) above as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates, and
- one or more oxidation bases.

The present invention also relates to a multi-compartment device, or kit, suitable for implementing the method according to the invention. Such a device includes:
- at least one compartment containing a composition comprising one or more compounds chosen from the compounds of formula (I) above as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates; and optionally one or more oxidation bases; And
- at least one compartment containing an oxidizing composition containing one or more chemical oxidizing agents.

The present invention also relates to particular novel compounds. These compounds are chosen from:
- those corresponding to one of the following formulas (IA), (IB) and (IC):
(AI) (IB) (IC)
the Ra, Rb, Rc, Rd, Re and Rf groups being as defined below; And
- and the compounds corresponding to the following formulas (22) and (58):
(22) (58)
X ⁺ designating a cation.

The invention also relates to a cosmetic composition comprising:
a) one or more compounds chosen from the compounds of formulas (IA), (IB), (IC), (22) and (58) above;
b) optionally, one or more oxidation bases.

Other characteristics, aspects, objects and advantages of the present invention will appear even more clearly on reading the description and the examples which follow.

Within the meaning of the invention, unless otherwise indicated:
- the limits of a range of values are included in this range, in particular in the expressions “between” and “ranging from … to …”;
- the expression “at least one” used in this description is equivalent to the expression “one or more” and can be substituted for it;
- By “keratin fibers” according to the present application, is meant human keratin fibers and more particularly the hair;
- by a "hydroxy group» denotes an —OH group;
- by "amino group» we designate an -NH group₂;
- the term "alkyl"denotes a hydrocarbon group, linear or branched, saturated or unsaturated, comprising from 1 to 6 carbon atoms, preferably the alkyl group is a C group₁to C₆saturated such as methyl, ethyl,not-propyl,iso-propyl,not-butyl,iso-butyl,ter-butyl, 2-butyl,not-pentyl, 2-pentyl, 3-pentyl, ornot-hexyl, more particularly the alkyl group is a C group₁to C₄saturated and linear such as methyl, or ethyl;
- the term "alkoxy» denotes an alkyl-oxy group (that is to say -O-alkyl) with alkyl as defined above, and preferably a methoxy or ethoxy group;
- by "hydroxyalkyl» means an alkyl group as defined above substituted by one or more hydroxy groups;
- by "(hydroxy)alkyl“means an alkyl or hydroxyalkyl group as defined above;
- by "hydroxyalkoxy“, means an alkoxy group as defined above substituted by one or more hydroxy groups, preferably a group (C₁-VS₆)alkoxy substituted with a hydroxy group such as β-hydroxyethoxy;
- by "(hydroxy)alkoxyis meant an alkoxy or hydroxyalkoxy group as defined previously;
- by“C-alkoxycarbonyl ₁ -VS ₃ »is meant a group of formula alkyl-O-CO- whose alkyl group comprises from 1 to 3 carbon atoms;
- by“C(hydroxy)alkoxycarbonyl ₁ -VS ₃ »means a C alkoxycarbonyl group₁-VS₃substituted or not by a hydroxy group;
- by group "(di)(hydroxy)alkyl(C ₁ -VS ₅ )aminocarbonyl”,means a C alkylaminocarbonyl group₁-VS₅optionally substituted with one or two hydroxy groups;
- by group“C-alkylaminocarbonyl ₁ -VS ₅ » denotes a group of formula alkyl-NH-CO- whose alkyl group comprises from 1 to 5 carbon atoms.

The compounds used in the invention

The process according to the invention uses one or more compounds chosen from those of formula (I) above, as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, their solvates; and their mixtures.

By addition salts is meant addition salts with an organic or inorganic acid or base, as well as organic or inorganic mono- or poly-cationic salts.

By addition salts with an acid is meant more particularly those chosen from addition salts with a cosmetically acceptable organic or inorganic acid such as salts derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H ₂ SO ₄ , iv) alkyl sulphonic acids: Alk-S(O) ₂ OH such as methyl sulphonic acid and ethyl sulphonic acid; y) arylsulphonic acids: Ar—S(O) ₂ OH such as benzene sulphonic acid and toluene sulphonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H ₃ PO ₄ ; xiii) acetic acid CH ₃ C(O)OH; xiv) triflic acid CF ₃ SO ₃ H, xv) tetrafluoroboric acid HBF ₄ , and xvi) hydriodic acid HI.

More particularly, the compounds of formula (I) can be salified with strong mineral acids such as HCl, HBr, HI, H ₂ SO ₄ , H ₃ PO ₄ , or organic acids such as, for example, acetic acid , lactic, tartaric, citric or succinic, benzenesulfonic, para-toluenesulfonic, formic, methane-sulfonic.

By addition salts with a base, is meant more particularly those chosen from addition salts with a cosmetically acceptable organic or inorganic base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines, or with a cosmetically acceptable anion.

The organic or inorganic mono- or poly-cationic salts can be chosen in particular from:
- ammoniums, (benz)imidazoliums;
- cationic oligomers or polymers;
- metal cations of copper, iron, magnesium, manganese, gold and zinc chosen from: Cu+, Cu2+, Fe2+, Fe3+, Mg2+, Mn4+, Au3+ and Zn2+; And
- Cationic salts of alkali and alkaline-earth metals such as Na ⁺ , K ⁺ , Li ⁺ , Ca ²⁺ .

The compounds of formula (I) can also be in the form of solvates, for example in the form of hydrate or solvate of a linear or branched alcohol such as ethanol or isopropanol.

According to a preferred embodiment, the compounds of formula (I) are chosen from those in which:
- R ₁ represents a hydrogen atom, a hydroxy group, or a linear C ₁ -C ₅ alkoxy group;
- R ₂ represents a hydrogen atom, a hydroxy group, a C ₁ -C ₃ alkoxy group, or a linear C ₁ -C ₅ alkyl group;
- R ₃ represents a hydroxy group, a (hydroxy)alkoxycarbonyl group in C ₁ -C ₃ , a (hydroxy)alkyl group in C ₁ -C ₃ , a (hydroxy)alkyl group (C ₁ -C ₃ )aminocarbonyl, a hydroxycarbonyl group (-COOH);
- R ₄ represents a hydrogen atom, or a linear or branched C ₁ -C ₄ alkyl group;
- R ₅ and R′ ₅ represent, independently of each other, a hydrogen atom, an amino group or a hydroxy group;
- R ₆ and R′ ₆ represent, independently of each other, a hydrogen atom or a linear C ₁ -C ₃ alkyl group;
Being heard that :
- R' ₅ and R ₃ cannot simultaneously represent a hydroxy group,
- If R ₃ represents a hydroxy group, R' ₅ represents a hydrogen atom.

According to a more preferred embodiment, the compounds of formula (I) are chosen from those in which:
-R₁represents a hydrogen atom, a hydroxy group, a methoxy group or an ethoxy group;
-R₂represents a hydrogen atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxy group,;
-R₃represents, a group hydroxy, methoxycarbonyl group, ethoxycarbonyl group, hydroxyethyloxycarbonyl group, hydroxymethyl group, hydroxyethylaminocarbonyl group, hydroxycarbonyl group (-COOH);
-R₄represents a hydrogen atom, or an alkyl group chosen from methyl, ethyl, isopropyl, n-butyl; and preferably R₄represents a hydrogen atom, an isopropyl group, or an n-butyl group;
-R₅and R'₅represent, independently of each other, a hydrogen atom, an amino group or a hydroxy group;
-R₆and R'₆represent, independently of one another, a hydrogen atom or a methyl group;
Being heard that :
- R'₅and R₃cannot simultaneously represent a hydroxy group,
- if R₃represents a hydroxy group, R'₅represents a hydrogen atom.

Preferably, the compound(s) of formula (I) are chosen from the compounds corresponding to formulas (1) to (117) below, their addition salts of organic or mineral acids, their optical isomers, their geometric isomers , their tautomers, and their solvates such as hydrates, and mixtures thereof:
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117

In the formulas above, X ⁺ represents a cation corresponding to a counterion resulting from the addition with an organic or inorganic base as defined previously, and preferably X ⁺ represents a sodium counterion (Na ⁺ ) or potassium (K ⁺ ).

According to a first variant, in formula (I), R ₅ , R ₆ , R′ ₅ and R′ ₆ all denote a hydrogen atom.

According to this variant, compounds 1, 4, 5, 7, 8, 9, 10, 13, 14, 15, 16, 17, 18, 19, 22, 23, 24, 25, 26, 27, 28 are preferred. 31, 32, 33, 34, 35, 36, 37, 40, 41, 42, 44, 46, 49, 50, 53, 54, 55, 58, 59, 61, 63, 64, 67, 68, 69, 71, 73, 76, 77, 78, 82, 85, 86, 87, 88, 89, 90, 91, 94, 95, 96, 97, 99, 100, 103, 104, 106, 107, 109, 112, 113, 114, and in particular compounds 21, 22, 30, 31, 35, 39, 40, 46, 47, 48, 49, 53, 54, 58, 67, 96, 97, 109, more particularly 21, 22, 30, 31, 35,39,40,96,97.

According to a second variant, only one of the radicals R ₅ and R′ ₅ denotes an amino radical. In this variant, the compound of formula (I) is preferably chosen from compounds 29, 30, 38, 47, 48, 75.

The compounds of formula (I) described above as well as their salts, their isomers and/or their solvates can be used pure or in the form of natural extracts containing at least one compound of formula (I). Among the natural extracts containing compounds of formula (I), mention may be made in particular of extracts of Epimedium grandiflorum, Epimedium macranthum Morr. and Decne , the seeds of Agrostemma githago, Saussurea laniceps.

More particularly preferred compounds are chosen from the compounds corresponding to the formulas below, their addition salts of organic or mineral acids, their optical isomers, their geometric isomers, their tautomers, and their solvates such as hydrates, and their mixtures:
22A 31A _ 35 40A _ 46 47 48 49A _ 53 54 58A _ 67A _ 96 97

Very particularly preferred compounds are the compounds corresponding to the formulas 31A, 35 and 40A.

The coloring process

The process according to the invention comprises a step i) which consists in applying to the keratin fibers a composition comprising or more compounds as described above.

According to a preferred embodiment, the method according to the invention also comprises the application to the keratin fibers of one or more oxidation bases, present in the composition applied in step i) or in a composition distinct applied to a step i′) implemented immediately before or immediately after step i).

Preferably, the oxidation base(s) are present in the composition applied in step i).

The oxidation bases can in particular be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and the corresponding addition salts.

Among the para-phenylenediamines, use may be made, for example, of para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para- phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N -dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl )amino-2-methylaniline, 4-N,N-bis(ß-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl- para -phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-fluoro- para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenedia mine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N- (β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine and the corresponding addition salts with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para- phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine , 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine and the corresponding acid addition salts.

Among the bis(phenyl)alkylenediamines, there are for example N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol, 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-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3' -methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and the corresponding addition salts.

Para-aminophenols include, for example, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol , 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol and the corresponding acid addition salts.

Examples of ortho-aminophenols include 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol and the corresponding addition salts.

Examples of heterocyclic bases include pyridine, pyrimidine and pyrazole derivatives.

Among the pyridine derivatives, there are the compounds described for example in patents GB 1,026,978 and GB 1,153,196, for example 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4-diaminopyridine and the corresponding addition salts.

Other pyridine-type oxidation bases useful in the present invention are the oxidation bases of 3-aminopyrazolo[1,5-a]pyridine or the corresponding addition salts described, for example, in the patent application FR 2 801 308. Examples which may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-morpholin-4 -ylpyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3-ylamine , (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3-aminopyrazolo [1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3 -ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[ 1, 5-a]pyrid-5-yl)(2-hydroxyethyl)-amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin-6-ol , 3-aminopyrazolo[1,5-a]pyridin-7-ol, 2-β-hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine; 2-(4-dimethylpiperazinium-1-yl)-3-amino-pyrazolo[1,5-a]pyridine; and the corresponding addition salts.

More particularly, the oxidation bases can be chosen from 3-aminopyrazolo-[1,5-a]-pyridines, preferably substituted on the carbon atom 2 by:
a) a (di)(C ₁ -C ₆ )(alkyl)amino group, said alkyl group possibly being substituted by at least one hydroxy, amino or imidazolium group;
b) a heterocycloalkyl group containing 5 to 7 members and 1 to 3 heteroatoms, optionally cationic, optionally substituted by one or more (C ₁ -C ₆ )alkyl groups, such as a di(C ₁ -C ₄ )alkylpiperazinium group; Or
c) a (C ₁ -C ₆ )alkoxy group optionally substituted by one or more hydroxy groups such as a β-hydroxyalkoxy group and the corresponding addition salts.

Among the pyrimidine derivatives are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine , 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

Among the pyrazole derivatives, there are the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FRA-2 733 749 and DE 195 43 988, such as 4, 5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole, 4 ,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3- dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3- tert -butyl-1-methylpyrazole, 4,5-diamino-1- tert -butyl -3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl- 3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl -1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'- aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3, 5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole and the corresponding addition salts. It is also possible to use 4,5-diamino-1-(β-methoxyethyl)pyrazole.

A 4,5-diaminopyrazole will preferably be used and even more preferably 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a corresponding salt.

The pyrazole derivatives which may also be mentioned include diamino-N,N-dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and the corresponding addition salts: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo [1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino -3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1, 2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-di-(2-hydroxyethyl)- 1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2 -amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino[1,2-a]pyrazol-1-one, 4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1, 2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one, 2,3-diamino-6- hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.

2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a corresponding salt will preferably be used.

Preferably, 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1 will be used. -one and/or a corresponding salt as heterocyclic bases.

The oxidation base(s) can advantageously represent 0.001% to 10% by weight and preferably 0.005% to 5% by weight, relative to the total weight of the composition comprising them.

According to one embodiment, the method according to the invention also comprises the application to the keratin fibers of one or more additional couplers, different from the compounds of formula (I) and their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates, present in the composition applied in step i) or in a separate composition applied in a step i′) implemented immediately before or immediately after step i).

Preferably, the additional coupler(s), when they are used, are present in the dye composition applied in step i).

The couplers can in particular be chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents as well as the corresponding addition salts.

Mention may be made, for example, of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(ß-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1 -dimethylaminobenzene, sesamol, 1-ß-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N -methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(ß-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2 ,6-bis(ß-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5 -one, 2,6-dimethyl-pyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6-methylpyrazolo[1,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(ß–hydroxy thyl)amino-2-methylphenol, 3-aminophenol, 3-amino-2-chloro-6-methylphenol, the corresponding addition salts with an acid and the corresponding mixtures.

Preferably, the additional oxidation coupler(s), if present, advantageously represent 0.001% to 10% by weight, more preferably 0.005% to 5% by weight, relative to the total weight of the composition comprising them.

In general, the addition salts of the oxidation bases and of the couplers which can be used are chosen from addition salts with an acid, such as the hydrochlorides, the hydrobromides, the sulphates, the citrates, the succinates, the tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

According to a preferred embodiment, the process according to the invention also comprises the application to the keratin fibers of one or more chemical oxidizing agent(s), present in the composition applied to the step i) or in a separate oxidizing composition applied in step ii) implemented before or after step i).

By “ chemical oxidizing agent ” is meant chemical oxidizing agents different from the oxygen in the air.

Preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulphate, peracids and oxidase enzymes (with their possible cofactors) such as peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; preferentially, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, persalts, and mixtures thereof.

Preferably, the chemical oxidizing agent(s) are present in a total content of between 0.001 and 50% by weight, more preferably between 0.05 and 30% by weight, even more preferably between 0.1 and 20% by weight, even more particularly between 1 and 15% by weight relative to the total weight of the composition comprising them.

According to a first variant of this embodiment, the method according to the invention comprises:
- a first step of mixing an oxidizing composition containing one or more chemical oxidizing agents, as described above, with a composition comprising the compound(s) chosen from the compounds of formula (I) and their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates, and optionally one or more coloring precursors, different from said compounds, chosen from oxidation bases and couplers; Then
- a step i) of application to the keratin fibers of the composition resulting from the mixture carried out in the preceding step.

In this variant, which constitutes the preferred variant, the dye composition applied in step i) is said to be “ready to use”.

According to a second variant of this embodiment, the method according to the invention comprises:
- a step i) of application to the keratin fibers of a composition comprising the compound(s) chosen from the compounds of formula (I) and their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates, and optionally one or more coloring precursors, different from said compounds, chosen from oxidation bases and couplers; And
- a step ii) of application to said fibers of an oxidizing composition containing one or more chemical oxidants, as described above;
step ii) being carried out before or after step i), preferably after.

In this variant, the keratin fibers can optionally be rinsed and/or washed between steps i) and ii).

In general, the composition applied in step i) is then left on the fibers for a period ranging, in general, from 1 minute to 1 hour, preferably from 5 minutes to 30 minutes.

The temperature during the process is conventionally between room temperature (between 15 to 25°C) and 80°C, preferably between room temperature and a temperature of 60°C.

Preferably, the composition is applied at ambient temperature.

At the end of the process, the keratin fibers are preferably rinsed with water, optionally subjected to washing with a shampoo followed by rinsing with water, before being dried or left to dry.

The cosmetic composition

The present invention also relates to a cosmetic composition.

According to a first variant, the composition according to the invention comprises:
a) one or more compounds, as described above, chosen from the compounds of formula (I) and their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates; And
b) one or more oxidation bases.

According to a second variant, the composition according to the invention comprises:
a) one or more compounds chosen from the compounds of formulas (IA), (IB), (IC), (22) and (58) above;
b) optionally, one or more oxidation bases.

The compound(s) a) are advantageously present in a total content of 0.001% to 5% by weight, more preferably 0.005% to 4% by weight, relative to the total weight of the cosmetic composition.

The oxidation base(s) are preferably chosen from those described above. They are advantageously present in a total content of 0.001% to 10% by weight and preferably 0.005% to 5% by weight, relative to the total weight of the cosmetic composition.

The cosmetic composition according to the invention may comprise, in addition to one, several additional couplers, different from the compounds of formula (I) and their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates.

The additional coupler(s), if present, are preferably chosen from those described above. They are advantageously present in a total content of 0.001% to 10% by weight, more preferably 0.005% to 5% by weight, relative to the total weight of the cosmetic composition.

The composition according to the present invention may optionally also comprise one or more direct dyes which can in particular be chosen from nitro dyes of the benzene series, azo direct dyes, methine direct dyes, and mixtures thereof. These direct dyes can be nonionic, anionic or cationic in nature.

The content of the direct dye(s), when they are present in the cosmetic composition according to the invention, preferably ranges from 0.001 to 10% by weight, and more preferably from 0.005 to 5% by weight, relative to the total weight of the composition.

The cosmetic composition according to the present invention may optionally also comprise one or more chemical oxidizing agents, as described above.

When they are present, the total content of the chemical oxidizing agent(s) is generally between 0.001 and 50% by weight, more preferably between 0.05 and 30% by weight, more preferably still between 0.1 and 20% by weight. , even more particularly between 1 and 15% by weight relative to the total weight of the cosmetic composition.

The cosmetic composition according to the invention advantageously comprises a carrier fluid suitable for coloring keratin fibres, chosen from cosmetically acceptable fluids. Said carrier fluid generally comprises one or more solvents chosen from water and a mixture of water and one or more organic solvents such as, for example, lower C ₁ to C ₄ alkanols, such as ethanol and isopropanol. , polyols such as propylene glycol, dipropylene glycol or glycerol, and polyol ethers such as dipropylene glycol monomethyl ether.

The content of said solvent(s) preferably ranges from 5 to 90% by weight, and more preferably from 10 to 80% by weight, relative to the total weight of the cosmetic composition.

The composition according to the present invention may optionally also comprise one or more adjuvants, preferably chosen from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof, anionic, cationic, nonionic, amphoteric, zwitterionic polymers and their mixtures, inorganic or organic thickening agents, and in particular anionic, cationic, nonionic or amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preservatives, opacifying agents.

Preferably, when they are present in the composition according to the invention, the adjuvant(s) generally represent an amount of between 0.01 and 20% by weight for each of them relative to the weight of the composition.

Of course, those skilled in the art will take care to choose this or these possible adjuvants in such a way that the advantageous properties intrinsically attached to the composition of the invention are not, or substantially not, altered by the addition or additions envisaged.

The pH of the cosmetic composition according to the invention is preferably between 3 and 12, more preferably between 5 and 11, and better still between 7 and 10. It can be adjusted to the desired value by means of one or more agents acidifying or alkalizing agents usually used in the field of dyeing keratinous fibers or alternatively with the aid of conventional buffer systems.

Among the acidifying agents that can be used, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

Among the alkalizing agents that can be used, mention may be made, by way of example, of ammonia, alkaline carbonates, (C ₁ -C ₆ )alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, hydroxides sodium or potassium and the compounds of formula (IV) below:

in which W is a (C ₁ -C ₁₀ )alkylene group, such as propylene, optionally substituted by one or more hydroxyl groups; Ra, Rb, Rc and Rd, which are identical or different, represent a hydrogen atom, a C ₁ to C ₄ alkyl radical or a C ₁ to C ₄ hydroxyalkyl radical.

The cosmetic composition according to the invention, whether or not it contains one or more oxidizing agents, can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for producing a coloring of keratin fibers, in particular human keratin fibers and in particular the hair.

New compounds
As indicated above, the present invention also relates to a compound chosen from:
- the compounds corresponding to one of the following formulas (IA), (IB) and (IC) as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates:
(AI) (IB) (IC)
in which :
Ra denotes a C ₂ -C ₃ (hydroxy)alkoxy group; or a (hydroxy)alkyl (C ₁ -C ₃ )amino group;
Rb denotes a hydrogen atom or a linear C ₁ -C _{5 alkyl group;}
Rc denotes a linear C ₁ -C ₅ alkyl group;
Rd denotes a hydroxy group, a C ₁ -C ₃ (hydrox)alkoxy group or a (C ₁ -C ₃ )amino (hydroxy)alkyl group;
Re denotes a hydroxy group or a linear C ₁ -C ₅ alkoxy group;
Rf denotes a (hydroxy)alkyl (C ₁ -C ₃ )amino group;
- and the compounds corresponding to the following formulas (22) and (58):
(22) (58)
in which X ⁺ denotes an organic or inorganic cation, and preferably X ⁺ represents a sodium (Na ⁺ ) or potassium (K ⁺ ) ion.

According to a preferred embodiment, in formula (IA) Ra denotes a methoxy, ethoxy, 2-hydroxyethoxy or 2-hydroxyethylamino group.

According to a preferred embodiment, in formula (IB):
Rb denotes a hydrogen atom or an ethyl group _;
Rc denotes a methyl group;
Rd denotes a hydroxy or 2-hydroxyethylamino group.

According to a preferred embodiment, in the formula (IC):
Re denotes a hydroxy, methoxy or ethoxy group;
Rf denotes a 2-hydroxyethylamino group.

Among the compounds of formula (IA), mention may be made of the compounds of formulas 95, 96, 97, 98 above, and the compounds of formulas 96 and 97 are preferred.

Among the compounds of formula (IB), mention may be made of the compounds of formulas 28, 29, 30, 31, 32, 33, 34, 35, 37, 38, 39, 40, 41, 42, 43, 44 above. , and compounds of formulas 30, 31, 35, 39, and 40 are preferred.

Among the compounds of formula (IC), mention may be made of the compounds of formulas 53, 62, 71. The compound of formula 53 is preferred.

Processes for the synthesis of the compounds of formulas (IA), (IB) and (IC)
The compounds of formula (IA) and (IB) defined above can be synthesized starting from an optionally substituted 1,3-dihydroxybenzene type derivative, or starting from optionally substituted 1,3,5-trihydroxybenzene (commonly called phloroglucinol) or its derivatives. The compounds of formula (IC) can be synthesized in the same way starting from corresponding benzene compounds.

The first step involves a lactonization reaction.

This reaction is generally carried out starting from a phenolic derivative and an acrylic acid unit, an acrylic acid ester, an acrylonitrile, a β-ethoxycarbonyloxy-propionitrile or even a 3-halogenopropionitrile-like unit. This reaction is carried out in two stages: the nucleophilic phenolic compound first reacts with the electrophilic agent mentioned above, then an intramolecular esterification reaction (lactonization) completes the reaction with the elimination of a water molecule. This so-called reversible step can be brought to completion easily by using an acid.

The reaction scheme is as follows:

The starting phenolic derivative is dissolved in a solvent, preferably apolar aprotic, having a boiling point of between 25° C. and 150° C., preferably between 50° C. and 125° C., even more preferably between 79° C. and 120° C., preferably chosen from toluene, benzene, heptane.

The reaction is carried out in an acid medium. The acid compound used can be an acid resin such as resins of the amberlite H, or IR, or even IRA type. The amount of acid used varies depending on the amount of aromatic (poly)hydroxy compound to be converted. Advantageously, when the acid compound is an acid resin, the amount of resin to be used is in a ratio of 0.1 to 4 relative to the amount of aromatic (poly)hydroxy compound, preferably in a ratio of 0.2 to 3 and even more preferably in a ratio of 0.2 to 1.

The reaction medium is stirred at the boiling point of the preferred solvents mentioned above.

The electrophile is generally added diluted in the reaction solvent and the amount of electrophile added is generally between 0.5 and 1.5 equivalents relative to the polyhydroxylated derivative.

The reaction time is between 10 minutes and 10 hours, preferably between 30 minutes and 9 hours, even more preferably between 1 hour and 6 hours.

The second step consists in reacting the lactone in the presence of an alkylating electrophile in order to generate the desired aromatic alkoxy derivative, according to the following reaction scheme:

The lactone previously obtained can thus be reacted in the presence of a solvent or mixture of a polar aprotic solvent and a mineral alkaline agent of carbonate type, as disclosed in the publication Chemical Communications, 2019, vol. 55, p. 2313 to 2316) at a temperature between 20°C and 100°C, preferably between 20°C and 75°C and more particularly between 20°C and 50°C.

The aprotic polar solvent or mixture of solvent(s) is generally chosen from tetrahydrofuran, 2-methyltetrahydrofuran, DMPU, DMF, sulfolane, dioxane, MTHP.

The mineral carbonate is preferably sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium.

The alkylating agent used is in particular a halogenated derivative, in which the halogen plays the role of leaving group. In general, this reaction is carried out at a temperature between 0°C and 150°C, preferably between 0°C and 120°C and even more preferably between 0°C and 90°C.

The reaction time is between 10 minutes and 10 hours, preferably between 30 minutes and 9 hours, even more preferably between 1 hour and 6 hours.

A reaction is followed by a post-treatment consisting in acidifying the reaction medium, carrying out an extraction with an appropriate organic solvent and then carrying out a purification to obtain the desired product.

The third step is to react a nucleophile to generate the desired phenolic derivative. One can carry out a hydrolysis, or an esterification, or an amidation, by opening of cycle.

The reaction scheme is as follows:

In the case where R₀represents a hydroxy group or O^-X⁺the general synthetic route is as follows:
The lactone previously obtained can be reacted in the presence of a polar (a)protic solvent or solvent mixture and a mineral alkaline agent of the hydroxide type in solution in water (Chemical Communications, 2019, vol. 55, p.2313 – 2316) at a temperature of between 20°C and 100°C, preferably between 20°C and 75°C and more particularly between 20°C and 50°C.
The solvent or mixture of polar (a)protic solvent(s) is generally chosen from tetrahydrofuran, 2-methyltetrahydrofuran, methanol, ethanol, isopropanol, water.
The mineral hydroxide is preferably sodium, potassium or lithium hydroxide. In the form of a powder, it is generally dissolved in water beforehand. The concentration of this solution is preferably between 0.5 M and 10 M, preferably between 1 M and 5 M and more particularly between 1 M and 3 M.
The reaction time is between 10 minutes and 10 hours, preferably between 30 minutes and 9 hours, even more preferably between 1 hour and 6 hours.
Then the reaction medium is acidified, which makes it possible to obtain the desired form (acid or salified).

In the case where R ₀ represents a C ₁ -C ₃ (hydrox)alkoxy group, the general synthetic route is as follows:
The previously obtained lactone can be reacted in the presence of a polar protic solvent which will play the role of the nucleophile and an acid (Synthesis, 2003, p. 27 – 29) at a temperature between -10°C and 80 °C preferably between 0°C and 60°C and more particularly between 10°C and 55°C.
The protic polar solvent is generally chosen from alcohols known to those skilled in the art such as methanol, ethanol, isopropanol, water.
The acid used, generally in a catalytic quantity, can be an acid resin such as resins of the amberlite H, or IR, or even IRA type. Advantageously, the amount of resin to be used is present in an amount of between 0.01% and 10%, even more preferably in an amount of between 0.1% and 1%.
The reaction time is between 10 minutes and 10 hours, preferably between 30' and 9 hours, even more preferably between 1 hour and 6 hours.

In the case where R ₀ represents a (hydroxy)alkyl (C ₁ -C ₃ )amino group , the general synthetic route is as follows:
The previously obtained lactone can be reacted in an (a)polar aprotic solvent with a nitrogenous nucleophile (primary or secondary amine, generally in a stoichiometric amount relative to the amount of lactone used) (Journal of the American Chemical Society, 1981 , vol. 103, p. 3910-3915) at a temperature between 0°C and 170°C, preferably between 10°C and 120°C and more particularly between 10°C and 100°C.
The aprotic polar solvent (a) is generally chosen from toluene, DMF, NMP, 1,4-dioxane, tetrahydrofuran, 2-methyltetrahydrofuran.
The reaction time is between 10 minutes and 10 hours, preferably between 30' and 9 hours, even more preferably between 1 hour and 6 hours.

The following examples serve to illustrate the invention without, however, being of a limiting nature.

EXAMPLES

I. Synthesis of compounds

Example 1: Synthesis of 3-(2,4-dihydroxy-6-methylphenyl)-N-(2-hydroxyethyl)propanamide (compound 35)
(35)

The reaction scheme is as follows:

Step 1 : Synthesis of 7-hydroxy-5-methyl-3,4-dihydro-2H-chromen-2-one (3)
Compound 1 (10g; 78.14 mmol; 1eq), 5g of amberlyst 15 suspended in 100ml of toluene. Heat to reflux. Compound 2 (6.19 g; 85.95 mmol; 1.1 eq) diluted in 100 ml of toluene is then added drop by drop very slowly.

Using a Dean Stark assembly, the reaction medium is heated for 6 hours. The latter is then filtered while hot and then left to return to room temperature. A solid crystallizes, the latter is filtered and then washed with dichloromethane. It is then dried in a desiccator at 40° C. under vacuum.

9.32g of a beige solid are obtained, corresponding to the 7-hydroxy-5-methyl-3,4-dihydro-2H-chromen-2-one product (3) after analysis. The yield is 74.7%.

Step 2 : synthesis of 3-(2,4-dihydroxy-6-methylphenyl)-N-(2-hydroxyethyl)propanamide (35)
Into a 25ml three-neck reactor fitted with a condenser, a thermometer and an argon inlet, introduce compound 3 (1g; 5.61 mmol; 1eq) in suspension in 12ml of toluene. Monoethanolamine (0.343g; 5.61mmol; 1eq) is then added. The reaction medium is heated at 95° C. for 6 h.

After cooling, wash with water. The aqueous phase is recovered, which is evaporated to dryness and then purified on a silica column. 847 mg of a pink viscous liquid corresponding to the compound of structure 35 are obtained. The yield of this step is 63%.

Example 2: Synthesis of sodium 3-(4-ethoxy-2-hydroxy-6-methylphenyl)propanoate (compound 40A)
(40A)

The reaction scheme is as follows:

Step 1 : Synthesis of 7-ethoxy-5-methyl-3,4-dihydro-2H-chromen-2-one (6)
0.627 g of compound 3 (3.519 mmol) is placed in suspension in 10 ml of sulfolane; potassium carbonate (0.678g; 4.909 mmol; 1.4 eq) is added then compound 5 (0.852g; 0.425 mmol; 1.2eq); the reaction medium is then heated at 90° C. for 4h30.

After cooling, 25 ml of water, 25 ml of AcOEt and 0.1 ml of 1N HCl are added until the pH of the aqueous phase is approximately 7-8. The organic phase is then washed with 25ml of water before being dried over sodium sulphate, filtered and then concentrated under vacuum. After purification on a silica column, 123 mg of a white solid are obtained, corresponding to compound 6 after analysis. The yield of the reaction is 16.9%.

Step 2 : Synthesis of sodium 3-(4-ethoxy-2-hydroxy-6-methylphenyl)propanoate (40A)
Compound 6 (123 mg; 0.596 mmol) is introduced into 1 ml of water in a 10 ml flask fitted with a cooler. After adding sodium hydroxide (0.024 g; 0.596 mmol, 1 eq), the reaction medium is left stirring at room temperature for 2 hours. The water is then eliminated with a rotavapor. The residue is then dried in a vacuum oven at 40°C. A pale pink solid corresponding to the sodium salt of compound 40 A (148 mg) is obtained.

Example 3: Synthesis of sodium 3-(2,4-dihydroxy-6-methylphenyl)propanoate (compound 31A)
(31A)

The reaction scheme is as follows:

In a 50 ml flask fitted with a cooler, compound 3 (2g; 11.2 mmol) is introduced into 20 ml of water and then sodium hydroxide (0.449 g; 11.2 mmol, 1eq) is added with a bath of ice.

The mixture is left to stir at room temperature for 20 h. After reaction, what has not been dissolved is filtered off and the water is eliminated using a rotavapor. The residue is dried in a vacuum oven at 40°C. 2.325g of a very hygroscopic pink solid corresponding to the sodium salt of compound 31A are obtained. The yield of the reaction is 95%.

Example 4: Synthesis of sodium 3-[2,4-dihydroxy-6-methyl-3-(propan-2-yl)phenyl]propanoate (compound 22A)
(22A)

The reaction scheme is as follows:

Step 1: Synthesis of 7-hydroxy-5-methyl-8-(propan-2-yl)-3,4-dihydro-2H-chromen-2-one (10)
Commercial compound 9 (1g; 6.02 mmol; 1eq), 30% by mass of amberlyst 15 ( 330 mg) which is suspended in 10 ml of toluene and then the reaction medium is heated to reflux. Compound 2 is then slowly added dropwise. (0.477g; 6.62mmol; 1.1eq) diluted in 2ml of toluene.

Using a Dean Stark assembly, the reaction medium is heated for 5 hours. After reaction, the reaction medium is filtered while hot, which is then allowed to return to ambient temperature. The solvents are subsequently evaporated to dryness and purification is then carried out on a silica column with the heptane/AcOEt: 7/3 system. 1.02 g of white crystals corresponding to compound 10 are obtained. The yield of the reaction is 77%.

2nd step : Synthesis of sodium 3-[2,4-dihydroxy-6-methyl-3-(propan-2-yl)phenyl]propanoate (22A)
In a 25 ml flask, compound 10 (1.02 g) is introduced into 10 ml of water and then sodium hydroxide (0.185 g; 4.63 mmol, 1eq) is added. The reaction medium is left to stir at room temperature for 24 hours. The water is then eliminated with a rotavapor. The residue thus obtained is dried in a vacuum oven at 40°C. 1.233g of a very hygroscopic purple solid corresponding to compound 22A is obtained. The yield of the reaction is quantitative.

Example 5: Synthesis of ethyl 3- (2,4,6- trihydroxyphenyl) propanoate (compound 96)
(96)

The reaction scheme is as follows:

Step 1 : Synthesis of 5,7-dihydroxy-3,4-dihydro-2H-chromen-2-one (13)
To a solution of phloroglucinol 12 (10 g, 79.3 mmol) in 100 mL of acetonitrile was added acrylic acid 2 (6.28 g, 87.3 mmol) and Amberlyst 15 (3. 2 g) in sequence. The mixture was refluxed for 24 h. After filtration, the filtrate was evaporated to dryness. The residue obtained was chromatographed on silica gel (dichloromethane/methanol=40/1) to yield 8.5 g of compound 13 in the form of a white solid. The yield is 60%.

Step 2: Synthesis of 5,7-dibenzyloxychroman-2-one (14)
To a solution of compound 13 (10 g, 55.6 mmol) in 80 mL of DMF at 0°C was added potassium carbonate (23 g, 166.7 mmol) and benzyl bromide (28.5 g , 166.7 mmol) in sequence. The mixture was returned to ambient temperature and left under stirring for 16 h. Then 300 ml of water was added and the organic phase was extracted with ethyl acetate. The combined organic phases were washed three times with water and brine, dried over anhydrous sodium sulphate, filtered and evaporated under vacuum. The resulting crude product was washed with diethyl ether, filtered and dried to provide 15g of compound 14 as a white solid. The yield is 75%.

Step 3: Synthesis of ethyl 3-(2,4-dibenzyloxy-6-hydroxy-phenyl)propanoate (15)
To a solution of compound 14 (4 g, 11.1 mmol) in 20 ml of ethanol was added Amberlyst 15 (0.4 g). The mixture was refluxed for 6 h. After filtration, the filtrate was evaporated to dryness. The residue was chromatographed on silica gel (petroleum ether/ethyl acetate=4/1) to yield 3.6 g of compound 15 in the form of a white solid. The yield is 80%.

Step 4: Synthesis of ethyl 3-(2,4,6-trihydroxyphenyl)propanoate (96)
To a solution of compound 15 (3.6 g, 8.87 mmol) in 20 mL of ethanol was added 0.36 g of 10% Pd/C. The mixture was hydrogenated at room temperature for 16 h using a hydrogen gas balloon. After filtration, the filtrate was evaporated to dryness. The residue was chromatographed on silica gel (dichloromethane/methanol=5/1) to give 1.8 g of compound 96 in the form of a white solid. The yield is 90%.

Example 6 : Synthesis of 2-hydroxyethyl 3-(2,4,6-trihydroxyphenyl)propanoate (compound 97)
(97)

The reaction scheme is as follows:

Step 1 : Synthesis of 2-hydroxyethyl 3-(2,4-dibenzyloxy-6-hydroxy-phenyl)propanoate (17)
To a solution of Compound 14 (2 g, 5.56 mmol) in 10 mL of ethylene glycol was added Amberlyst 15 (0.4 g). The mixture was heated at 80°C for 6 h. After cooling, 50 ml of water was added and the organic phase was extracted three times with ethyl acetate. The combined organic phases were washed three times with brine, dried over anhydrous sodium sulphate, filtered and evaporated under vacuum. The residue was chromatographed on silica gel (petroleum ether/ethyl acetate=2/1) to give 1.75 g of compound 17 in the form of a white solid. The yield is 75%.

Step 2: Synthesis of 2-hydroxyethyl 3-(2,4,6-trihydroxyphenyl)propanoate (97)

To a solution of compound 17 (1.75 g, 3.95 mmol) in 20 mL of methanol was added 0.16 g of 10% Pd/C. The mixture was hydrogenated at room temperature for 16 h using a hydrogen gas balloon. After filtration, the filtrate was evaporated to dryness. The residue was chromatographed on silica gel (dichloromethane/methanol=5/1) to give 0.9 g of compound 97 in the form of a white solid. The yield is 94%.

II. Examples of hair dyes

a) Compositions implemented
The compositions used in this example were prepared from a basic cosmetic composition (A) comprising the ingredients whose contents are indicated in percentage by weight relative to the total weight of each composition, in the table below. Composition A Ethyl alcohol 20.8 Sodium metabisulphite in 35% aqueous solution 0.23 my Pentasodium salt of diethylene-triamine-pentaacetic acid in 40% aqueous solution 0.48 my C ₈ -C ₁₀ alkyl polyglucoside in 60% aqueous solution 3.6 my Benzyl alcohol 2.0 Polyethylene glycol with 8 ethylene oxide units 3.0 _NH4Cl 4.32 Ammonia at 20% NH ₃ 2.94 Oxidation base 5.10 ^-3 mole Coupler 5.10 ^-3 mole Water Qsp 100

ma = active ingredient

The composition above was made with each of the oxidation bases below.
Oxidation base 4-aminophenylamine dihydrochloride B1 2-Methylbenzene-1,4-diamine dihydrochloride B2 2-(4,5-diamino-1H-pyrazol-1-yl)ethanol sulfate B3 2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one dimethanesulfonate B4 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride B5 4-(3-Aminopyrazolo[1,5-a]pyridin-2-yl)-1,1-dimethylpiperazin-1-ium chloride hydrochloride B6

A first series of compositions (A1) to (A6) were prepared, using compound 35 as coupler, and each of the respective oxidation bases B1 to B6.

A second series of compositions (A7) to (A12) were prepared, using compound 31A as coupler, and each of the respective oxidation bases B1 to B6.

A composition (A13) was finally produced using compound 40A as coupler and oxidation base B6.

b) Procedure
At the time of use, each of the compositions (A1) to (A13) was mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained.
Each mixture thus obtained was applied to locks of natural white hair at 90% white. After an exposure time of 45 minutes, the locks were rinsed with water. They are then washed with a standard shampoo, rinsed again, then dried.

vs)Colorimetric results obtained
The results in terms of the color of the wicks are indicated in the table below
Composition Color A1: compound 35 + B1 chestnut A2: compound 35 + B2 chestnut A3: compound 35 + B3 pale purple A4: compound 35 + B4 beige A5: compound 35 + B5 purple A6: compound 35 + B6 Grey blue A7: compound 31A + B1 dark gray A8: compound 31A + B2 gray A9: compound 31A + B3 pale purple A10: compound 31A + B4 beige A11: compound 31A + B5 purple red A12: compound 31A + B6 Grey blue A13: compound 40A + B6 dark blue

The colors observed with these couplers are close to those observed with the reference couplers (resorcinol or 2-methylresorcinol).

III. Comparative example

The following combinations were compared:
Compound 31A + B1 versus Compound (a) + B1
Compound 40A + B6 versus Compound (a) + B6
the compound (a) being resorcinol.

These combinations were implemented in the basic cosmetic composition (A) described in Example II.a). The procedure is that described in Example II.b) above.

Colorimetric results (system L, a, b):
The colorimetric data of each of the locks are then measured with a Minolta CM-3610d spectrophotometer. In this L* a* b* system, L* represents the brightness, a* indicates the green/red color axis and b* the blue/yellow color axis. The higher the value of L*, the lighter or less intense the color. Conversely, the lower the value of L*, the darker or more intense the color. The higher the value of a* the more red the shade and the higher the value of b* the more yellow the shade.

The results obtained are shown in the table below.
Compositions tested I* 40A+B6 47.34 (a) + B6 50.09 31A+B1 45.15 (a) + B1 47.69

It appears from the results of the table that the keratin fibers colored with the compounds of formula (I) according to the invention are colored more intensely than with the comparative compound (a).

Claims (20)

Process for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising at least one step i) of applying to said keratin fibers a composition comprising one or more compounds chosen from the compounds of formula (I) following, as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates:
(I)
formula (I) in which:
-R₁represents a hydrogen atom, a hydroxy group, or a C-linear alkoxy group₁-VS₅optionally substituted by one or more groups chosen from a hydroxy group and an amino group;
-R₂represents a hydrogen atom, a hydroxy group, a C (hydroxy)alkoxy group₁-VS₃, or a linear C-alkyl group₁-VS₅optionally substituted by one or more groups chosen from a hydroxy group and an amino group;
-R₃represents a hydrogen atom, a hydroxy group, a C (hydroxy)alkyl group₁-VS₅, a C alkoxy group₁-VS₃, an alkoxy group (C₁-VS₃)methyloxy, a C (hydroxy)alkoxycarbonyl group₁-VS₃, a (di)((hydroxy)alkyl C₁-VS₅)aminocarbonyl, a hydroxycarbonyl (-COOH) group, an -SO group₃H, or a -PO group₃H;
-R₄represents a hydrogen atom or a C (hydroxy)alkyl group₁-VS₆linear or branched;
-R₅and R'₅represent, independently of one another, a hydrogen atom, an amino group, a hydroxy group, a hydroxycarbonyl group (-COOH), a linear C-alkyl group₁-VS₃optionally substituted by a hydroxycarbonyl radical (-COOH) or an aromatic group, such as in particular a phenyl radical optionally substituted by a hydroxy group;
-R₆and R'₆represent, independently of each other, a hydrogen atom or a linear C-alkyl group₁-VS₃. Process according to Claim 1, characterized in that the compounds of formula (I) are chosen from those in which:
- R ₁ represents a hydrogen atom, a hydroxy group, or a linear C ₁ -C ₅ alkoxy group;
- R ₂ represents a hydrogen atom, a hydroxy group, a C ₁ -C ₃ alkoxy group, or a linear C ₁ -C ₅ alkyl group;
- R ₃ represents a hydroxy group, a (hydroxy)alkoxycarbonyl group in C ₁ -C ₃ , a (hydroxy)alkyl group in C ₁ -C ₃ , a (hydroxy)alkyl group (C ₁ -C ₃ )aminocarbonyl, a hydroxycarbonyl group (-COOH);
- R ₄ represents a hydrogen atom, or a linear or branched C ₁ -C ₄ alkyl group;
- R ₅ and R′ ₅ represent, independently of each other, a hydrogen atom, an amino group or a hydroxy group;
- R ₆ and R′ ₆ represent, independently of each other, a hydrogen atom or a linear C ₁ -C ₃ alkyl group;
Being heard that :
- R' ₅ and R ₃ cannot simultaneously represent a hydroxy group,
- If R ₃ represents a hydroxy group, R' ₅ represents a hydrogen atom. Process according to any one of the preceding claims, characterized in that the compounds of formula (I) are chosen from those in which:
-R₁represents a hydrogen atom, a hydroxy group, a methoxy group or an ethoxy group;
-R₂represents a hydrogen atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxy group,;
-R₃represents, a group hydroxy, methoxycarbonyl group, ethoxycarbonyl group, hydroxyethyloxycarbonyl group, hydroxymethyl group, hydroxyethylaminocarbonyl group, hydroxycarbonyl group (-COOH);
-R₄represents a hydrogen atom, or an alkyl group chosen from methyl, ethyl, isopropyl, n-butyl; and preferably R₄represents a hydrogen atom, an isopropyl group, or an n-butyl group;
-R₅and R'₅represent, independently of each other, a hydrogen atom, an amino group or a hydroxy group;
-R₆and R'₆represent, independently of one another, a hydrogen atom or a methyl group;
Being heard that :
- R'₅and R₃cannot simultaneously represent a hydroxy group,
- if R₃represents a hydroxy group, R'₅represents a hydrogen atom. Process according to any one of the preceding claims, characterized in that the compound or compounds of formula (I) are chosen from the compounds corresponding to the following formulas (1) to (117), their addition salts of organic acids or minerals, their optical isomers, their geometric isomers, their tautomers, and their solvates such as hydrates, and their mixtures:
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 in which X⁺represents a cation, preferably sodium (Na⁺) or potassium (K⁺). Process according to the preceding claim, characterized in that the compound(s) of formula (I) are chosen from the compounds corresponding to the following formulae, their addition salts of organic or inorganic acids, their optical isomers, their geometric isomers, their tautomers, and their solvates such as hydrates, and mixtures thereof:
22A 31A _ 35 40A _ 46 47 48 49A _ 53 54 58A _ 67A _ 96 97 and preferably from compounds corresponding to formulas 31A, 35 and 40A. Process according to any one of the preceding claims, characterized in that the compounds of formula (I) are chosen from those in which R ₅ , R ₆ , R' ₅ and R' ₆ all denote a hydrogen atom. Process according to any one of Claims 1 to 5, characterized in that the compounds of formula (I) are chosen from those in which only one of the radicals R ₅ and R' ₅ denotes an amino radical. Process according to any one of the preceding claims, characterized in that it also comprises the application to the keratin fibers of one or more oxidation bases, present(s) in the composition applied in stage i) or in a separate composition applied at step i′) implemented immediately before or immediately after step i); and preferably present in the composition applied in step i). Process according to any one of the preceding claims, characterized in that it also comprises the application to the keratin fibers of one or more chemical oxidizing agent(s), present in the composition applied in step i) or in a separate oxidizing composition applied in step ii) implemented before or after step i). Method according to the preceding claim, characterized in that it comprises:
- a first step of mixing an oxidizing composition containing one or more chemical oxidizing agents with a composition comprising the compound(s) chosen from the compounds of formula (I) and their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates, and optionally one or more coloring precursors, different from said compounds, chosen from oxidation bases and couplers; Then
- a step i) of application to the keratin fibers of the composition resulting from the mixture carried out in the preceding step. Process according to either of Claims 8 and 9, characterized in that the chemical oxidizing agent or agents are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes (with their possible cofactors) such as peroxidases, 2-electron oxidoreductases such as uricases and oxygenases with 4 electrons such as laccases, and their mixtures; preferably from hydrogen peroxide, persalts, and mixtures thereof. Cosmetic composition comprising:
- one or more compounds chosen from the compounds of formula (I) as defined in any one of claims 1 to 7 as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates, And
- one or more oxidation bases Composition according to the preceding claim, characterized in that the oxidation base or bases are chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and salts of corresponding additions. Composition according to one of Claims 12 and 13, characterized in that it additionally comprises one or more chemical oxidizing agents, preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes (with their possible cofactors) such as peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; and more preferably from hydrogen peroxide, persalts, and mixtures thereof. Compound chosen from:
- the compounds corresponding to one of the following formulas (IA), (IB) and (IC) as well as their addition salts, their optical isomers, their geometric isomers, their tautomers, and their solvates:
(IA) (IB) (IC)
in which :
Ra denotes a C ₂ -C ₃ (hydroxy)alkoxy group; or a (hydroxy)alkyl (C ₁ -C ₃ )amino group;
Rb denotes a hydrogen atom or a linear C ₁ -C _{5 alkyl group;}
Rc denotes a linear C ₁ -C ₅ alkyl group;
Rd denotes a hydroxy group, a C ₁ -C ₃ (hydrox)alkoxy group or a (C ₁ -C ₃ )amino (hydroxy)alkyl group;
Re denotes a hydroxy group or a linear C ₁ -C ₅ alkoxy group;
Rf denotes a (hydroxy)alkyl (C ₁ -C ₃ )amino group;
- and the compounds corresponding to the following formulas (22) and (58):
(22) (58)
in which X ⁺ denotes an organic or inorganic cation, and preferably X ⁺ represents a sodium (Na ⁺ ) or potassium (K ⁺ ) ion. Compound corresponding to formula (IA) according to claim 15, preferably in which Ra denotes a methoxy, ethoxy, 2-hydroxyethoxy or 2-hydroxyethylamino group. Compound corresponding to formula (IB) according to claim 15, preferably in which:
Rb denotes a hydrogen atom or an ethyl group _;
Rc denotes a methyl group;
Rd denotes a hydroxy or 2-hydroxyethylamino group. Compound corresponding to the formula (IC) according to claim 15, preferably in which:
Re denotes a hydroxy, methoxy or ethoxy group;
Rf denotes a 2-hydroxyethylamino group. Cosmetic composition comprising:
a) one or more compounds chosen from the compounds of formulas (IA), (IB), (IC), (22) and (58) as defined in any one of claims 15 to 18;
b) optionally, one or more oxidation bases. Multi-compartment device comprising:
- at least one compartment containing a composition comprising one or more compounds chosen from the compounds of formula (I) as defined in any one of claims 1 to 7 as well as their addition salts, their optical isomers, their geometric isomers , their tautomers, and their solvates; and optionally one or more oxidation bases; And
- at least one compartment containing an oxidizing composition containing one or more chemical oxidizing agents.