FR3060563A1 - DIRECT COLORANT WITH STYRYL AND CARBONATE GROUPS, COMPOSITION COMPRISING AT LEAST ONE SUCH COLOR, PROCESS FOR USE AND USE - Google Patents

Abstract

The present invention relates to a process for the dyeing and / or lightening of keratinous substances, in particular the hair, comprising the application to said materials of a cosmetic composition comprising one or more compounds of formula (I), as well as their forms. tautomers, optical isomers, geometric isomers, their addition salts with an acid or a base, organic or inorganic, and / or their solvates: formula (I) in which ALK, p, L, A, Ra, Rb, Rc, Rd, and Q are as defined in the description The invention also relates to the use of these particular compounds for the dyeing and / or lightening of keratin fibers.

Description

© Publication no .: 3,060,563 (to be used only for reproduction orders)

©) National registration number: 16 62758 ® FRENCH REPUBLIC

NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY

COURBEVOIE

©) Int Cl ⁸ : C 07 D 405/06 (2017.01), A 61 K 8/41, A 61 Q 5/10, 5/08

A1 PATENT APPLICATION

©) Date of filing: 19.12.16. ©) Applicant (s): L'OREAL Société anonyme— FR. (30) Priority: (72) Inventor (s): BLAISE CHRISTIAN and MESSA- VUSSU ABEL. (43) Date of public availability of the request: 22.06.18 Bulletin 18/25. (56) List of documents cited in the report preliminary research: Refer to end of present booklet @) References to other national documents ©) Holder (s): L'OREAL Société anonyme. related: ©) Extension request (s): ©) Agent (s): CASALONGA.

FR 3 060 563 - A1 (04 / DIRECT DYE WITH STYRYLE AND CARBONATE GROUPS, COMPOSITION COMPRISING AT LEAST ONE SUCH DYE, PROCESS FOR USE AND USE.

The present invention relates to a process for coloring keratin fibers.

tion and / or lightening of keratin materials, in particular of the hair, comprising the application to said materials of a cosmetic composition comprising one or more compounds of formula (I), as well as their tautomeric forms, optical isomers, geometric isomers , their addition salts with an acid or a base, organic or mineral, and / or their solvates:

formula (I) in which ALK, p, L, A, R _a , R _b R _c , Rd, and Q are as defined in the description

The invention also relates to the use of these particular compounds for coloring and / or lightening

i

Direct dye with styryl and carbonate groups, composition comprising at least one such dye, process for use and use

The present invention relates to direct dyes with styryl and carbonate groups, of formula (I), (la), or (Ib), as well as their use for the coloring and / or lightening of keratin fibers, in particular keratin fibers human such as hair.

It is known to dye keratin fibers, and in particular the hair, with cosmetic compositions containing one or more direct dyes, according to a process known as “direct coloring”.

The method conventionally used in direct coloring consists in applying to the keratin fibers one or more direct dyes, or dye molecules, having an affinity for said fibers, in letting them pause, then in rinsing the fibers. The direct dyes hitherto used are generally benzene nitro dyes, anthraquinone dyes, nitropyridine dyes, azo, xanthene, acridine, azine dyes or triarylmethane dyes.

However, the resulting colorings are temporary or semi-permanent colorations, because the nature of the interactions which bind the direct dyes to the keratinous fiber, and their desorption from the surface and / or of the core of the fiber are responsible for their low dye power and their poor resistance to washing, bad weather or perspiration.

These dyes also have the disadvantage of lacking stability with regard to light, due to the low resistance of the chromophore compared to photochemical attacks, which tends to lead to a fading in time of the coloring of the keratin fibers.

There is therefore a real need for direct dyes which have a good rise in color, good compatibility with oxidizing agents, and good resistance to shampoo, to light and to sweat, and which make it possible to obtain a coloring without selectivity of the color between the root and the point, which have good chromaticity and / or intensity.

The Applicant has thus surprisingly discovered that compounds of formula (I) as defined below, as well as their tautomeric forms, optical isomers, geometric isomers, their addition salts with an acid or a base, organic or inorganic , and / or their solvates, made it possible to achieve this (these) goal (s).

The subject of the invention is therefore a process for dyeing and / or lightening keratin materials, in particular keratin fibers, preferably human fibers such as the hair, comprising the application to said materials of a cosmetic composition comprising one or more several compounds of formula (I), as well as their tautomeric forms, optical isomers, geometric isomers, their addition salts with an acid or a base, organic or mineral, and / or their solvates:

R.

R, b

(I) formula (I) in which:

> ALK represents a divalent, linear or branched, saturated or unsaturated hydrocarbon chain, comprising from 1 to 20 carbon atoms, optionally substituted, optionally interrupted by one or more heteroatoms or groups chosen from: -O-, —C (O) - , -N (R) -, and -N ⁺ (R) (R ') - or their combinations such and>

-N (R) -C (O) -, -C (O) -N (R) -, -OC (O) -, -C (O) -O-, preferably ALK represents a chain (Ci-Ci8 ) alkylene; with R, and R ’, identical or different, representing a hydrogen atom or a (Ci-C4) alkyl group optionally substituted by one or more hydroxy groups;

> p is 1, 2 or 3, preferably 1;

> L represents:

i) a group comprising from 2 to 10 carbon and / or nitrogen atoms, comprising an unsaturation or several conjugated unsaturations, which allows the electrons of A to pass to the pyridinium group of the molecule; or ii) (hetero) arylene;

> A represents an optionally substituted (hetero) aryl group, preferably substituted by one or more atoms or groups chosen from:

o C1-C6 linear or branched alkyl, optionally substituted by one or more atoms or groups chosen from:

halogen such as chlorine, hydroxy -OH, thiol -SH, (Ci-C4) alkoxy, amino -N (R) -R ', with R and R ’identical or different, being as defined above;

o -N (R) (R '), R and R', identical or different, being as defined above;

o 5 or 6-membered heterocycloalkyl; o 5 or 6-membered heteroaryl;

-OR o, R representing a hydrogen atom, an alkyl group-alkyl, preferably Ci-C _4, linear or branched;

o a halogen atom, or o -CN;

R _a , Rb, Rc, and Rd _; identical or different, represent a hydrogen atom, a group (Ci-C6alkyl, or then two contiguous groups R _a and Rb and / or Rb and R _c , and / or R _c , and Rd _; form together with the atom of carbon which carry them an optionally substituted (hetero) aryl group comprising from 5 to 7 members, preferably the optionally substituted benzo group;

> Q 'represents one or more anionic counter-ions allowing to reach the electro-neutrality of the molecule.

The compounds of formula (I) according to the invention thus make it possible to lead to colorations which are resistant to the various aggressions which the keratin fibers can undergo, such as bad weather, light, washing and perspiration.

In addition, the direct dyes according to the invention make it possible to dye the keratin fibers satisfactorily, in particular by leading to powerful, chromatic, not very selective dyes, and / or with a good rise in color.

The direct dyes according to the invention also have the advantage of being light stable and can be used in the presence of an oxidizing agent which facilitates their use in cosmetic lightening direct dye compositions based on oxidizing agents.

In other words, the direct dyes according to the present invention lead to stubborn coloring and are compatible with cosmetic compositions which are intended to lighten keratin fibers.

In addition, these dyes can be used to lighten dark keratin materials, in particular with a tone height less than or equal to 6, preferably less than or equal to 4, while remaining tenacious and this without the use of reducing agent or agent. chemical oxidant.

Another object of the present invention relates to the use of one or more compounds of formula (I) as defined above, for the coloring of keratin materials, in particular keratin fibers, preferably human keratin fibers such as the hair. .

The present invention also relates to a cosmetic composition for dyeing keratin fibers, in particular human keratin fibers such as the hair, comprising one or more compounds of formula (I) as defined above, preferably comprising one or more several compounds of formula (la) and / or (Ib) as well as their tautomeric forms, optical isomers, geometric isomers, their addition salts with an acid or a base, organic or inorganic, and / or their solvates;

(la) (Ib)

Formulas (la) and (Ib) in which:

> n represents an integer ranging from 1 to 12;

> Ri, R ₂ , R3, R4 and R5 represent independently of each other:

o a hydrogen atom, o a C1-C6 alkyl group, linear or branched, optionally substituted by:

-OH,

-N (R) (R '), R and R' representing a hydrogen atom, a C1-C4 alkyl group, linear or branched, optionally substituted by -OH, o -N (R) (R '), R and R 'being as defined above, o -OR, R representing a hydrogen atom, a C1-C6, preferably C1-C4 alkyl group, linear or branched, o a halogen atom, or o -CN; and> R _a and Rb represent a hydrogen atom, or R _a and Rb form together with the carbon atoms which carry them, a benzo group:

The invention also relates to the use of said cosmetic composition for coloring keratin fibers, in particular human keratin fibers such as the hair.

The invention further relates to the compounds of formula (la) and (lb) as defined above as well as their means of preparation.

According to one embodiment, the process for treating keratin materials of the invention is carried out to color and lighten said dark materials, in particular keratin fibers, in particular human keratin fibers such as the hair, a process in which one applies to said materials (i) a cosmetic composition free from an oxidizing agent and (ii) a cosmetic composition comprising one or more oxidizing agents; the compositions (i) and (ii) being applied to said keratin materials sequentially or simultaneously for a time sufficient to obtain the desired lightening, after which the fibers are rinsed, they are optionally washed with shampoo, rinsed again and dried or the resulting fibers are allowed to dry.

According to a preferred embodiment, the process for treating dark keratin materials of the invention is carried out to color and lighten said materials, in particular keratin fibers, in particular human keratin fibers such as hair with a tone height less than or equal to 6, more particularly less than or equal to 4, in which a cosmetic composition free of oxidizing agent is applied to said materials (i); composition (i) being applied to said keratin materials for a time sufficient to obtain the desired lightening, after which the fibers are rinsed, optionally washed with shampoo, rinsed again and the resulting fibers are dried or allowed to dry, it being understood that the process does not use a chemical oxidizing agent.

The present invention also relates to a device with several compartments for implementing the method according to the invention.

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

Within the meaning of the present invention, and unless a different indication is given:

the dyes according to the invention absorb light in the visible,

ie at a wavelength X _a bs particularly inclusive between 400 and 700 nm;

the “fluorescent” dyes according to the invention of formula (I) are dyes for which L represents - (CR ^s = CR ^h -) t-, particularly -CR ^s = CR ^h - and preferably L represents -CH = CHet dyes of formula (la) or (Ib) which are capable of absorbing light in the visible at a wavelength Xabs particularly between 400 and 800 nm and reemitting in the visible at a greater wavelength Xem than that absorbed between 400 and 800 nm; the difference in the absorption and emission wavelength also called Stoke's shift or Stoke's shift is between 1 nm and 100 nm. More preferably, the fluorescent dyes of the invention are dyes capable of absorbing at a wavelength X _a b _S of between 420 nm and 550 nm and of reemitting in the visible at a wavelength Xem of between 470 and 600 nm;

a "hydrocarbon chain" represents a divalent C1-C20 acyclic hydrocarbon chain; particularly in C1-C10, more particularly in linear Ci-Cg; optionally substituted by one or more groups, identical or different, chosen from i) hydroxy, ii) (Ci-C2) alkoxy, iii) (poly) hydroxy (C2-C4) alkoxy (di) (Ci-C ₂ ) (alkyl ) amino, iv) R ^a -Z ^a -C (Z ^b ) -Z ^c -, and v) R ^a -Z ^a -S (O), - Z ^c with Z ^a , Z ^b , identical or different, representing oxygen, sulfur, or NR ^a ', Z ^c is a bond, oxygen, sulfur, or NR ^a; R ^a , representing an alkali metal, a hydrogen atom, an alkyl group or else is absent if another part of the cationic molecule and R ^a 'representing a hydrogen atom or an alkyl group and t is 1 or 2; more particularly the groups iv) are chosen from carboxylate -C (O) -O 'or -C (O) -O', Q ⁺ represents a cationic counter-ion, carboxyl -C (O) OH, guanidino H ₂ HC (NH ₂ ) -N (H) -, amidino H ₂ HC (NH ₂ ) -, (thio) ureo H ₂ NC (O) -N (H) - and H ₂ NC (S) -N (H) -, aminocarbonyl C (O) -NRa ' ₂ or aminothiocarbonyl -C (S) -NRa'₂; carbamoyl Ra'-C (O) -N (Ra ') - or thiocarbamoyl Ra'-C (S) -N (Ra') - with Ra ', identical or different, representing a hydrogen atom or a group (Ci-C4 ) alkyl;

"(hetero) aryl" means the aryl and heteroaryl groups;

by “(hetero) arylene” is meant the arylene and heteroarylene groups i.e. a divalent aryl or divalent heteroaryl group;

the “aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radical can be substituted by at least one substituent carried by a carbon atom, chosen from:

a C ₁ -C ₆ , preferably C ₁ -C ₄ alkyl radical, optionally substituted by one or more radicals chosen from hydroxy, C ₁ -C ₂ alkoxy, (poly) C ₂ -C ₄ alkoxy, acylamino radicals, amino substituted by two identical or different C1-C4 alkyl radicals, optionally carrying at least one hydroxy group or, the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7-membered, preferably 5 or 6-membered, saturated or unsaturated, optionally substituted, optionally comprising another heteroatom identical or different from nitrogen;

- a halogen atom;

- a hydroxy or thiol group;

- a C1-C6 alkoxy or C1-C6 alkylthio radical;

- a C ₂ -C 6 (poly) hydroxyalkoxy radical;

- an amino radical;

- a 5- or 6-membered heterocycloalkyl radical, preferably morpholino, piperazino, piperidino, or pyrolidino optionally substituted by a (C1-C4) alkyl radical, preferably methyl;

- a heteroaryl radical with 5 or 6 members, preferably imidazolyl, and optionally substituted by a (C1-C4) alkyl radical, preferably methyl;

- an amino radical substituted by one or two alkyl radicals, identical or different, in C 1 -C 6 optionally carrying at least:

i) a hydroxy group, ii) an amino group optionally substituted by one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 chain links, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen, iii) a quaternary ammonium group -N ⁺ R'R "R"", M 'for which R', R", R '”, Identical or different, represent a hydrogen atom, or a C1-C4 alkyl group; and M 'represents an anionic counterion, iv) or a 5- or 6-membered heteroaryl radical optionally cationic, preferably imidazolium, and optionally substituted by a (C1-C4) alkyl radical, preferably methyl;

- an acylamino radical (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxy group and the radical R 'is an alkyl radical _C-2;

ίο

- a carbamoyl radical ((R) 2N-C (O) -) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxy group;

- an alkylsulfonylamino radical (R'-S (O) 2-N (R) -) in which the radical R represents a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxy group and the radical R 'represents a C1-C4 alkyl radical, a phenyl radical;

- an aminosulfonyl radical ((R) 2N-S (O) 2-) in which the radicals R, which may or may not be identical, represent a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxy group ,

- a carboxylic radical in acid or salified form (preferably with an alkali metal or ammonium, substituted or not);

- a cyano group;

- a nitro or nitroso group;

- a polyhaloalkyl group, preferably trifluoromethyl;

the cyclic or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent chosen from groups:

- hydroxy;

C1-C4 alkoxy, (poly) hydroxy-C2-C4 alkoxy; C1-C4 alkyl;

alkylcarbonylamino (RC (O) -N (R ') -) in which the radical R' is a hydrogen atom, a C1-C4 alkyl radical optionally carrying at least one hydroxy group and the radical R is a radical C1-C2 alkyl, amino optionally substituted by one or two identical or different C1-C4 alkyl groups themselves optionally bearing at least one hydroxy group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen;

alkylcarbonyloxy (RC (O) -O-) in which the radical R is a C1-C4 alkyl radical, amino group optionally substituted by one or two identical or different C1-C4 alkyl groups themselves optionally bearing at least a hydroxy group, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen;

alkoxycarbonyl (RXC (O) -) in which the radical R is a C1-C4 alkoxy radical, X is an oxygen atom, or an amino group optionally substituted by a C1-C4 alkyl group itself optionally bearing '' at least one hydroxy group, said alkyl radical possibly forming with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from l 'nitrogen;

a cyclic, heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, can also be substituted by one or more oxo groups;

a hydrocarbon chain is unsaturated when it has one or more double bonds and / or one or more triple bonds;

an “aryl” radical represents a mono or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;

a “heteroaryl radical” represents a mono or polycyclic group, condensed or not, optionally cationic, comprising from 5 to 22 links, from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom, and of which at least one cycle is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyle, pyrilyl, pyrazoyltriazyle, pyridyle, pyridinoimidazolyle, pyrrolyle, quinolyle, tétrazolyle, thiadiazolyle, thiazolyle, thiazolopyridinyle, thiazoylimidazolyle, thiazylimyl, thiopyrylyly;

a “heterocyclic radical” is a radical which may contain one or two unsaturations but not aromatic, mono or polycyclic, condensed or not, containing from 5 to 22 links, comprising from 1 to 6 heteroatoms chosen from the nitrogen atom, oxygen, sulfur and selenium;

a “heterocycloalkyl radical” is a heterocyclic radical comprising at least one saturated ring;

an "alkyl radical" is a linear or branched Ci-Cio hydrocarbon radical, in particular in Ci-Cg, more particularly in Ci-C6, preferably in C1-C4;

an “alkenylene radical” is a divalent unsaturated hydrocarbon radical as defined above which can contain from 1 to 4 double bonds -C = C-, conjugated or not; particularly the alkenylene group contains 1 or 2 unsaturation (s);

the expression “optionally substituted” attributed to the alkyl radical implies that said alkyl radical can be substituted by one or more radicals chosen from the radicals i) hydroxy, ii) C1-C4 alkoxy, iii) acylamino, iv) amino optionally substituted by one or two, identical or different, C1-C4 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom carrying them, a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom different from or not from nitrogen; v) or a quaternary ammonium group

N ⁺ R'R "R"',M' for which R ', R ", R"', identical or different, represent a hydrogen atom or an alkyl group CiC ₄ or -N ⁺ R'R then ”R '” forms a heteroaryl such as imidazolium optionally substituted by a C1-C4 alkyl group, and M' represents the counterion of the organic acid, mineral or of the corresponding halide;

an “alkoxy radical” is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in Ci-Cg preferably in Ci-C6;

when the alkoxy group is optionally substituted, this means that the alkyl group is optionally substituted as defined above;

by “which lets the electrons from A to the pyridinium group of the molecule” means a divalent unsaturated group which allows the electronic transition n-7i * and / or π-π * allowing an electronic delocalization on either side of A the following groups may be mentioned for pyridinium -N = N-, -C (R ^f ) = N-, -N = C (R ^f ) -, - (CR ^g = CR ^h -) _t -, -C ( R ^f ) = NN (R ^h ) -, -N (R ^h ) -N = C (R ^f ) -, with R ^f , R ^g and R ^h , identical or different, represent a hydrogen atom, or a (C1-C4) alkyl group, preferably hydrogen, and t is 1, 2, 3 or 4, preferably t is 1;

"pitch" is the unit known to hair professionals, and published in the book "Science of hair treatments" by Charles ZVIAK 1988, Ed. Masson, p. 215 and 278, the pitch of the tone ranges from 1 (black) to 10 (light light blonde), a unit corresponding to a tone, the higher the number, the lighter the shade;

the “dark” keratin fiber is a keratin fiber which has a luminescence L * encrypted in the CIEL system * a * b *, less than or equal to 45 and preferably less than or equal to 40, knowing moreover that L * = 0 is equivalent black and L * = 100 white;

"dark" hair is naturally or artificially dark hair whose pitch is less than or equal to 6 (dark blonde) and preferably less than or equal to 4 (chestnut). Artificially colored hair is hair whose color has been modified by a coloring treatment, for example coloring with direct dyes or oxidation dyes;

by “organic or mineral acid salt” is meant more particularly the salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) acids alkylsulfonic: Alk-S (O) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 20H such as benzene sulfonic acid and toluene sulfonic 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 H3PO4; xiii) acetic acid CH ₃ C (O) -OH; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF ₄ ;

by “anionic counterion” is meant an anion or an anionic group derived from an organic or mineral acid counterbalancing the cationic charge of the dye; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates including Ci-C6 alkyl sulfonates: Alk-S (O) 2O 'such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S (O) 2O 'such as benzenesulfonate and toluenesulfonate or tosylate; v) the carboxylates Alk-C (O) -OH with Alk representing a group (CiC6alkyl optionally substituted by one or more hydroxy or carboxylate groups such as citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-O-S (O) O 'such as methysulfate and ethyl sulfate; x) arylsulfates: Ar-O3060563

S (O) O such as benzenesulfate and toluenesulfate; xi) alkoxysulfates: Alk-OS (O) 2O such as methoxy sulfate and ethoxysulfate; xii) aryloxysulfates: Ar-OS (O) 2O, xiii) phosphates O = P (OH) ₂ -O ', O = P (O) ₂ -OH O = P (O) ₃ , HO- [P ( O) (O)] _W P (O) (O) 2 with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate, and xvii) disulfate (O =) 2S (O) 2 or SO4 ² 'and monosulfate HSO4';

the anionic counter ion, derived from organic or mineral acid salt, ensures the electroneutrality of the molecule: thus it is understood that when the anion comprises several anionic charges then the same anion can be used for the electroneutrality of several cationic groups in the same molecule or can be used for the electroneutrality of several molecules; for example a dye of formula (I), (la) or (lb) which contains two cationic groups can contain either two anionic counter ions "monoloaded" or either contains an anionic counterion "bicharged" such as (O =) ₂ S (O) ₂ or O = P (O) ₂ -OH;

In particular, anionic counterions such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; a hydrogen sulfate; a linear or branched C 1 -C 6 alkyl sulphate, such as the methyl sulphate or ethyl sulphate ion; carbonates and hydrogen carbonates; salts of carboxylic acids such as formate, acetate, citrate, tartrate, oxalate; linear or branched C1-C6 alkylsulfonates such as the methylsulfonate ion; arylsulfonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C1-C4 alkyl radicals such as, for example, 4toluylsulfonate; alkyl sulfonyls such as mesylate;

By “chemical oxidizing agent” is meant any oxidizing agent other than air oxygen conventionally used in the field. Thus, mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, as well as the enzymes among which mention may be made of peroxidases, oxidoreductases with 2 electrons such as uricases and oxygenases with 4 electrons such as laccases. Preferably, the chemical oxidizing agent is hydrogen peroxide.

Furthermore, the addition salts which can be used in the context of the invention are in particular chosen from addition salts with a cosmetically acceptable base such as the basifying agents as defined below such as the alkali metal hydroxides such as sodium hydroxide , potash, ammonia, amines or alkanolamines.

the expression "at least one" is equivalent to "one or more"; and the limits of a domain of values are included in this domain, in particular in the expressions "included between" and "going from ... to ...";

the expression "inclusive" means that the limits of the range are part of the defined interval;

The compounds of formula (I), (la) or (Ib) can be optionally salified with organic or mineral acids as defined above.

They can also be in the form of solvates, for example, a hydrate or a solvate of linear or branched alcohol such as ethanol or isopropanol.

In the context of the invention, the term “derivative of formula (I), (la), and (Ib)” means all geometric or optical mesomeric or isomeric forms.

According to a particular embodiment of the invention, the compounds of formula (I) are as taken together or separately:

> ALK represents a divalent, linear or branched, saturated hydrocarbon chain comprising from 1 to 18 carbon atoms, unsubstituted;

> p is 1, 2 or 3, preferably 1;

> L represents a group - (CH = CH-) _t -, and t is 1, or 2, preferably t is 1; or> A represents a (hetero) aryl group optionally substituted by one or more atoms or groups chosen from:

o C1-C6 linear or branched alkyl, optionally substituted by one or more atoms or groups chosen from:

hydroxy -OH, (Ci-C4) alkoxy, amino -N (R) -R ', with R and R' identical or different, being as defined above, o -N (R) (R '), R and R ', identical or different, being as defined above, o -OR, R representing a hydrogen atom, a C1-C6, preferably C1-C4 alkyl group, linear or branched, and o -CN; and / or> R _a , Rb Re and Rd _; identical or different, represent a hydrogen atom, a group (Ci-C6alkyl, and / or two contiguous groups R _a and Rb, form together with the carbon atom which carry them a benzo group.

According to one embodiment of the invention, the compounds of formula (I) are chosen from the compounds of formula (la) and (Ib) as defined above.

Preferably the compounds of formula (la) or (Ib) are such that, taken together or separately:

> n represents an integer ranging from 1 to 6, particularly from 1 to 4;

> Ri, R ₂ , R3, R4 and R5 represent independently of each other:

o a hydrogen atom, o a C1-C4, preferably C1-C4 alkyl group, linear or branched, optionally substituted by:

-OH,

-N (R) (R '), R and R' having the same meanings as above, o -N (R) (R '), R and R' having the same meanings as above, or o -OR, R having the same meanings as above;

and> R _a and Rb a hydrogen atom, or R _a and Rb form, with the carbon atoms which carry them, a benzo ring.

More particularly, the compounds of formula (la) or (Ib) are such that, taken together or separately:

> n represents an integer ranging from 1 to 4, such as 1 or 2;

> Ri, R2, R3, R4 and R5 represent independently of each other:

o a hydrogen atom, o -N (R) (R '), R and R' representing a hydrogen atom, a C1-C4 alkyl group, linear or branched, optionally substituted by -OH, o -OR , R representing a C1-C6, preferably C1-C4 alkyl group, linear or branched; and / or> R _a and Rb represent a hydrogen atom.

In a particularly preferred embodiment, the compounds formula (I) are chosen from those of formula (la) or (Ib) in which taken together or separately:

. n = l, • Ri, R2, R3, R4 and R5 represent independently of each other:

o a hydrogen atom, or o -OR, R representing a C1-C4 alkyl group, linear or branched, and> R _a and Rb represent a hydrogen atom.

According to a preferred embodiment of the invention, the compound or compounds of formula (I), (la) or (Ib) as defined above are chosen from the following compounds 1 to 4:

OH

with Q as defined above, preferably Q represents 410 CH ₃ -phenyl-SO ₃ .

The process for the synthesis of dyes of formula (I), (la) and (Ib) of the invention is described below.

The dyes of the invention are synthesized from commercial reagents or synthesizable from methods known to those skilled in the art. These include Angewandte chemie, International Edition (2004), 43 (46), 6331-6335.

The compounds of formula (I) can be obtained according to scheme 1 of synthesis below:

HO — ALK

O

Y i) (1)

Q — O — ALK

O (2)

AT-

R,

Ü) Scheme 1 in which ALK, p, R _a , R _b , R _c , Ra, L, A are as defined above, and Q represents a leaving group.

This process consists in a first step of reacting alcohol carbonate (1) which is functionalized by a leaving group, in particular an arylsulfonate such as tosyl, by reacting the reagent (1) in an aprotic solvent, in particular halogenated such as dichloromethane or tetrahydrofuran (THF), in the presence of a preferably organic base to lead, in particular at low temperature (0 ° C to 5 ° C) according to step i) to the compound (2) which reacts with at least one equivalent of pyridine (3) preferably by heating at reflux of solvent to yield the compound of formula (I). The latter can be purified by conventional purification methods such as chromatography and / or recrystallization.

According to a variant, the compounds of formula (la) of the invention are prepared according to the following synthetic scheme 2:

i) thionyl halide · aprotic solvent c

vs

(a) O = S '' Il o

scheme 2 in which R _a , Rb, Ri, R2, R3, R4, R5 and n being as defined above, and X represents an oxygen or sulfur atom.

In this operating mode, during the first step i) the alcohol carbonate is functionalized by a leaving group of tosyl type by the action of thionyl halide such as para-toluenesulfonic acid chloride, preferably in a solvent aprotic type, which can be apolar, in particular halogenated such as dichloromethane, or polar such as tetrahydrofuran (THF), in the presence of a preferably organic tertiary base such as triethylamine or 7V, 7V-diisopropylethylamine, a temperature between 0 and 5 ° C. During the second step ii), the carbonate derivative thus functionalized (1 ′) is then reacted with at least one equivalent of the 4-methylpyridine compound substituted with R _a and Rb, preferably heated to a temperature between 60 ° C. and 100 ° C, or at solvent reflux to yield the compound (2 '). The compound obtained is then reacted, during step iii), with an equivalent of (thio) aldehyde in a protic solvent such as, methanol or ethanol, in the presence of at least one equivalent of a organic base preferably chosen from pyrrolidine acetate or a tertiary base such as triethylamine or N, Ndiisopropylamine, preferably at a temperature between 30 ° C and 100 ° C to lead to the compound ( a) belonging to the general formula (la). The compound (a) can then be purified by conventional purification methods such as by chromatography and / or recrystallization.

According to another variant, the compounds of formula (Ib) of the invention are prepared according to the following synthetic scheme 3:

Scheme 3 in which R _a , Rb, Ri, R2, R3, R4, R5, X and n being as defined above, Ri and R'i; identical or different, representing a (Ci-Ce) alkyl, arylalkyl group such as benzyl or aryl, and Hal, and Hal ', identical or different, represent a halogen atom, preferably chlorine.

In this procedure, during the first step i) the pyridine 4-haloalkyl (4) is reacted in a preferably aprotic polar solvent, such as THF, in the presence of a hydride such as, for example, 'sodium hydride, preferably at low temperature ie at a temperature between -5 ° C and 5 ° C in the presence of a phosphonic acid diester, such as diethyl phosphonate. The phosphonate compound (5) thus obtained is then, during step ii), reacted in a polar solvent, preferably aprotic, such as tetrahydrofuran, in the presence of a hydride such as sodium hydride, and an equivalent of aldehyde at a temperature between 5 ° C and 60 ° C. The compound (6) thus obtained is reacted with the carbonate derivative (1 ′) previously prepared, in a polar protic solvent such as, for example, methanol, ethanol or isopropanol, at a temperature between 30 ° C and 110 ° C to lead to the obtaining of the compound of the compound (I'b) belonging to the general formula (Ib). The compound (I’b) can then be purified by conventional purification methods such as by chromatography and / or recrystallization.

The present invention also relates to a composition for dyeing keratin fibers comprising, in a medium suitable for dyeing in particular keratin fibers such as the hair, one or more compounds of formula (I), (la) and / or ( Ib) as defined above, as well as their optical isomers, geometric isomers, tautomers, their addition salts with an acid or a base, and their solvates such as hydrates.

According to a particular embodiment of the invention, the compound or compounds of formula (I), (la) and / or (Ib) as defined above represent from 0.001 to 10% by weight, more particularly from 0.005 to 6% by weight relative to the total weight of the composition.

The medium suitable for dyeing, also called dye support, generally comprises water or a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water.

More particularly, the organic solvents are chosen from monoalcohols or diols, linear or branched, preferably saturated, comprising from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2- methyl 2,4pentanediol), neopentylglycol and 3-methyl-1,5-pentanediol; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol; glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol; as well as the alkyl ethers of diethylene glycol, in particular in C1-C4, such as for example, the monoethyl ether or the monobutyl ether of diethylene glycol, alone or as a mixture.

The usual solvents described above, if they are present, usually represent from 1 to 40% by weight, more preferably from 5 to 30% by weight, relative to the total weight of the composition.

The composition comprising the dye (s) of formula (I), (la) or (Ib) as defined above of the process of the invention may also contain one or more additional direct dyes other than the direct dyes of formula (I) , (Ha) or (Ilb) according to the invention.

These direct dyes are for example chosen from those conventionally used in direct dyeing, and among which mention may be made of all the aromatic and / or non-aromatic dyes of common use such as neutral, nitrous, acid or cationic direct dyes, direct dyes azo neutral, acid or cationic, natural direct dyes, direct dye quinones and in particular neutral anthraquinone, acid or cationic, direct dyes azine, triarylmethanic, indoamine, methines, styriles, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and the fluorescent dyes different from the dyes of formula (I), (la) or (lb)

Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes and in particular the poultices or extracts based on henna.

According to the invention, the additional direct dye (s) used according to the invention preferably represent from 0.001% to 10% by weight approximately of the total weight of the dye composition comprising the dye (s) of formula (I), (la) or (Ib) as defined above and even more preferably from 0.05% to 5% by weight approximately.

The composition comprising the dye (s) of formula (I), (la) or (Ib) as defined above of the process of the invention may also contain one or more oxidation bases and / or one or more couplers conventionally used for tincture of keratin fibers.

Among the oxidation bases, there may be mentioned paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

Among these couplers, mention may in particular be made of metaphenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

The coupler (s) are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

The oxidation base or bases present in the dye composition are generally present each in an amount between 0.001 to 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6% by weight.

In general, the addition salts of the oxidation bases and of the couplers which can be used in the context of the invention are in particular chosen from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as soda, potash, ammonia, amines or alkanolamines.

According to a particular embodiment, the composition of the process of the invention contains at least one oxidation base and optionally at least one coupler as defined above.

The process of the invention can also implement another composition which comprises one or more chemical oxidizing agent (s). By chemical oxidizing agent is meant chemical oxidizing agents other than air oxygen such as those described above.

The use of hydrogen peroxide is particularly preferred.

The content of chemical oxidizing agent (s) is generally inclusive between 1 and 40% by weight, relative to the weight of the composition, preferably between 1 and 20% by weight relative to the weight of the composition the container (s).

According to a preferred embodiment of the invention, the composition of the process of the invention does not contain a chemical oxidizing agent. In particular, the process of the invention does not use a chemical oxidizing agent. Preferably neither the composition nor the process contain or use an oxidation base and / or a coupler.

The dye composition useful in the context of the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative thickeners anionic, cationic, nonionic and amphoteric, 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.

These above adjuvants 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.

Of course, those skilled in the art will take care to choose this or these optional complementary compounds in such a way that the advantageous properties intrinsically attached to the dye composition useful in the context of the invention are not, or not substantially, altered by the planned addition (s).

The pH of the dye composition useful in the context of the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.

Among the acidifying agents, there may be mentioned, by way of example, mineral acids such as for example hydrochloric acid, nitric acid, sulfuric acid or organic acids such as for example compounds comprising at least one acid function carboxylic like acetic acid, tartaric acid, citric acid, lactic acid, a sulfonic acid function, a phosphonic acid function or a phosphoric acid function.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (VI) below:

N —W — N

R ^u (VI) in which W is a group (C 1 -C 6 alkylene optionally substituted by one or more hydroxyl group or a C 1 -C 4 alkyl radical; R ^a , R ^b , R ^c and R ^d , identical or different, represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.

The oxidizing agent can be used to obtain a simultaneous lightening of the keratin fibers (lightening coloring) and / or when the composition contains oxidation bases or couplers.

In the case where the oxidizing agent or the oxidizing agents will be used in the dye composition or in the process according to the invention, its amount or their amount will preferably vary from 5 to 100% by weight, better still from 50 to 100% by weight relative to the total weight of the composition which comprises them.

The dye composition useful in the context of the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin materials, in particular fibers. keratin, and in particular human such as the hair.

The coloring process according to the invention comprises the application to the keratin materials, of at least one dye composition as defined above.

When a chemical oxidizing agent is used, it may be present in the composition of the invention. It can also be applied separately, in pre or post treatment.

Preferably, the composition of the invention does not include a chemical oxidizing agent.

Preferably, the process for treating keratin materials of the invention does not use a chemical oxidizing agent.

Preferably, the composition of the invention does not include a reducing agent.

Preferably, the process for treating keratin materials of the invention does not use a reducing agent.

According to a particular embodiment, the coloring process is used to color clear keratin materials, more particularly clear keratin fibers preferably with a pitch greater than 6 (HT> 6) which consists in applying to said materials a cosmetic composition comprising at least one direct dye chosen from those of formulas (I), (la) and (Ib) as defined above.

According to another particular embodiment of the invention, the coloring and lightening process is carried out on dark keratinous material, more particularly dark keratinous fibers preferably with a tone tone less than or equal to 6, more preferably less than or equal to 4, such as 2 which consists in applying to said materials a cosmetic composition comprising at least one direct dye chosen from those of formulas (I), (la) and (Ib) as defined above.

The pause time of the coloring composition, ie comprising the dye (s) of formula (I), (la) or (Ib) as defined above is inclusive between 3 minutes and 1 hour, preferably between 5 minutes and 40 minutes, more preferably between 10 and 30 minutes.

The application of the coloring composition (s) is generally carried out at room temperature. However, it can be carried out at temperatures varying from 20 to 180 ° C., preferably between 25 and 55 ° C.

The coloring and / or lightening process according to the invention can be followed by shampooing with a conventional shampoo and / or drying the keratin fibers.

According to a particular embodiment, neither the composition nor the process of the invention uses a reducing agent.

According to a particular embodiment, neither the composition nor the process of the invention uses a chemical oxidizing agent. The application of the composition of the invention may or may not be followed by rinsing.

The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

Example 1: Synthesis of 4 - methylbenzenesulfonate of l - [(2-oxo-l, 3dioxo lan-4-yl) methyl] -4 - [- 2- (2,4,5-tri methoxy phenyl) ethenyl] pyridinium

(a) Synthesis of (2-oxo-E3-dioxolan-4-yl) methyl 4-methylbenzenesulfonate

In a three-liter three-necked flask equipped with a thermometer, a refrigerant, an argon inlet, a bubbler, an addition funnel and a magnetic stirrer, 50 g of 4-hydroxymethyl [1,3] dioxalan-2-one (0.423 mole) in 300ml of dichloromethane. The medium was cooled to 0-5 ° C with an ice bath. A solution containing 80.7 grams of paratoluene sulfonic acid chloride (0.423 mole) in 100 ml of dichloromethane was then added dropwise, keeping the temperature below 5 ° C. The reaction medium was allowed to return, with stirring, at room temperature and then heated to reflux for 1 h 30 min. We then added

81.2 ml of diisopropylethylamine (0.466 mole). The reaction medium was then heated at reflux for 3 hours, following the manipulation by thin layer chromatography (TLC) in dichloromethane / methanol 9: 1, development under UV. The reaction medium was left at room temperature for 18 hours and then concentrated under reduced pressure. The oil thus obtained was poured into an Erlenmeyer flask containing 1.5 liters of water and 200 ml of 37% hydrochloric acid. The precipitate thus obtained was stirred for 30 minutes then filtered through a cotton cloth and washed thoroughly with water. The precipitate was then dried under vacuum in the presence of P2O5 to a constant weight of 105 grams. The precipitate was crushed into a powder using a mortar and washed in an Erlenmeyer flask containing 500 ml of ethanol with stirring for 1 h. The precipitate was then filtered through cotton cloth and washed thoroughly with ethanol. The precipitate was then dried under vacuum in the presence of P2O5 to a constant weight. There was thus obtained a white powder, conforming to NMR.

(b) Synthesis of diethyl (pyridin-4-yl-methyl) phosphonate

Ethanol

25 grams of sodium hydride (0.607 mole) were placed in a 500 ml three-necked flask equipped with a water cooler, an argon inlet, a bubbler, a thermometer and a magnetic stirrer ) 60% suspended in paraffin, previously washed 3 times with 100 ml of heptane, containing 200 ml of ethanol cooled by an ice bath. The reaction medium was stirred for 15 minutes at a temperature between -5 and 5 ° C. Using an addition funnel, 47 ml of diethyl phosphite (0.364 mol) were added dropwise so as to maintain the temperature at 0 ° C. When the addition was complete, the reaction medium was kept stirring and allowed to come to room temperature. 39.84 grams of 4-picolyl chloride (0.243 mole) were then added dropwise. When the addition is complete, the reaction medium is left under stirring at ambient temperature, following the reaction by TLC in dichloromethane / methanol 9: 1, development under UV light. The reaction medium was then evaporated under reduced pressure, and the residue obtained was filtered through sintered glass. The filtrate obtained was taken up in 200 ml of ethyl acetate and washed with 200 ml of water and 200 ml of a saturated solution of sodium chloride. The organic phase was dried over magnesium sulfate and concentrated under reduced pressure to yield the expected product. There was thus obtained a dark brown oil, conforming to NMR.

(c) Synthesis of 4- [2- (2,4.5-trimethoxyphenyllethenyllpyridine o

I

NOT

O

k.

o

o

Na-H

O

THF

NOT /

/

O

O \

2.1 grams of hydride were placed in a 250 ml three-necked flask, equipped with an argon inlet, a bubbler, an air cooler, a thermometer and a magnetic stirrer. sodium (0.052 mole), previously washed with 3 times 30 ml of heptane, in 50 ml of tetrahydrofuran. A solution containing 8 grams of diethyl (pyridin-4-ylmethyl) phosphonate (0.035 mol) previously prepared, was then added in 100 ml of tetrahydrofuran. We then added

8.2 grams of 2,4,5-trimethoxybenzaldehyde (0.042 mole). The reaction mixture was then brought to 50 ° C. with stirring, following the reaction by TLC in dichloromethane / methanol 9: 1, development under UV. The final product was obtained by purification on a silica column. The reaction medium was evaporated under reduced pressure and purified on a normal phase column eluting with dichloromethane / methanol 10: 0 to 9: 1. The fractions containing the expected product were combined and concentrated under reduced pressure and the residue obtained was dried under vacuum in the presence of P2O5 to a constant weight.

An off-white powder was thus obtained, compliant in mass spectrometry and NMR.

(d) Synthesis of l - [(2-oxo-L3-dioxolan-4yl] methyl-4- [2- (2,4,5-trimethoxyphenyl) ethenyllpyridinium methylbenzenesulfonate

o

In a 50 ml three-necked flask equipped with a water cooler, an argon inlet, a bubbler, a thermometer, and a magnetic stirrer, 5 grams of 4- [2- (2,4,5-trimethoxyphenyl) ethenyl] pyridine (0.013 mole) then 3.5 grams of (2-oxo-1,3-dioxolan-4yl) methyl 4-methylbenzenesulfonate (0.013 mole) were added in 10 ml of methanol. The reaction medium was then heated to reflux, following the manipulation by TLC in dichloromethane / methanol / ammonia 84: 15: 1. The reaction medium was evaporated under reduced pressure and the residue obtained was purified on a normal phase column eluting with dichloromethane / methanol 9: 1 to 8: 2. The fractions containing the expected compound were combined, evaporated under reduced pressure and then the residue was dried under vacuum in the presence of P2O5 to a constant weight. A red powder was thus obtained, compliant in mass spectrometry (MS) and NMR.

Comparative example 1

The comparative compound is the disulfide dye with the following structure:

Example 2

A dye composition according to the invention was prepared (composition 1), comprising:

- 0.5% by weight of the compound of Example 1, and

- 99.5% by weight of water relative to the weight of the composition.

Two comparative compositions were prepared with composition 1 in which the compound 1 was replaced by the compound of Comparative Example 1 at a concentration of 0.25% by mass and one at 0.5% by mass. A comparative composition similar to composition 1 in which the compound of Example 1 has been replaced by the compound of Comparative Example 1.

10.0 g of each of the compositions (composition 1 and comparative compositions) are applied to a lock of 1.0 g of gray hair containing 90% white hairs. After 20 minutes of laying at 37 ° C., the lock is rinsed, washed with a standard shampoo and then dried.

The application of a shampoo was renewed 20 times.

Colorimetric measurements

The L * a * b * values were measured with a MINOLTA CM-3610d spectrophotometer and used with the Spectra Magix NX software.

In this L * a * b * system, the three parameters respectively designate L *: the intensity of the color, a *: indicates the green / red color axis and b *: the blue / yellow color axis. For intensity, the lower the value, the darker and more intense the color.

The color remanence is represented by the color difference ΔΕ between the colored wick then shampooed with a single shampoo and the colored and shampooed wick with 20 successive shampoos: the higher the value of ΔΕ, the lower the remanence of the shampoos. This value is calculated from the following equation (i):

ΔΕ = V (L * -L ₀ *) ² + (a * -a0 *) ² + (b * -b0 *) ² _(j)

In equation (i), L *, a * and b * represent the values measured on the colored lock of hair then shampooed with 10 or 20 successive shampoos, and L _o *, ao * and bo * represent the values measured on the lock of colored hair then shampooed with a single shampoo.

The chromaticity of the color is calculated according to the following equation (ii):

C * = V (a *) ² + (b *) ²

In which a * and b * represent the values measured on locks of treated hair. The higher the value of C *, the greater the chromaticity of the color.

The colors obtained on strands thus treated and the values of L *, a *, and b * are collated in the table below:

Compositions Number of shampoos L * at* b * VS* ΔΕ * Composition 1 1 45.76 25.03 51.10 56.90 5.07 20 48.93 22.27 53.95 58.36 Comparative composition, 0.25% 1 56.74 15 53.68 55.73 10.4 20 59.88 8.40 46.28 47.03 Comparative composition, 0.5% 1 55.17 17 54.86 57.43 13 20 59.65 8.68 47.26 48.34

ΔΕ * = color difference between 1 and 20 successive shampoos

The results obtained show that the coloration obtained with the compound of the invention is more resistant to shampoos. Furthermore, the colors obtained with the compound of the invention are significantly more chromatic and more intense compared.

that

Claims (19)

1. Process for dyeing and / or lightening keratin materials, in particular keratin fibers, preferably human fibers such as the hair, comprising the application to said materials of a cosmetic composition comprising one or more compounds of formula (I ), as well as their tautomeric forms, optical isomers, geometric isomers, their addition salts with an acid or a base, organic or mineral, and / or their solvates: (I) formula (I) in which: > ALK represents a divalent, linear or branched, saturated or unsaturated hydrocarbon chain, comprising from 1 to 20 carbon atoms, optionally substituted, optionally interrupted by one or more heteroatoms or groups chosen from: -O-, —C (O) - , -N (R) -, and -N ⁺ (R) (R ') - or combinations thereof -N (R) -C (O) -, -C (O) -N (R) -, -OC (O) -, -C (O) -O-, preferably ALK represents a chain (Ci-Ci8 ) alkylene; with R, and R ’, identical or different, representing a hydrogen atom or a (Ci-C4) alkyl group optionally substituted by one or more hydroxy groups; > p is 1, 2 or 3, preferably 1; > L represents: i) a group comprising from 2 to 10 carbon and / or nitrogen atoms, comprising an unsaturation or several conjugated unsaturations, which allows the electrons of A to pass to the pyridinium group of the molecule; or ii) (hetero) arylene; > A represents an optionally substituted (hetero) aryl group, preferably substituted by one or more atoms or groups chosen from: o C1-C6 linear or branched alkyl, optionally substituted by one or more atoms or groups chosen from: halogen such as chlorine, hydroxy -OH, thiol -SH, (Ci-C4) alkoxy, amino -N (R) -R ', with R and R ’identical or different, being as defined above; o -N (R) (R '), R and R', identical or different, being as defined above; o 5 or 6-membered heterocycloalkyl; o 5 or 6-membered heteroaryl; o -OR, R representing a hydrogen atom, a C1-C6, preferably C1-C4 alkyl group, linear or branched; o a halogen atom, or o -CN; and> Ra, Rb Re and Rd _; identical or different, represent a hydrogen atom, a (Ci-Ce) alkyl group, or else two contiguous groups R _a and Rb and / or Rb and R _c , and / or R _c , and Rd _; together with the carbon atom which carries them form an optionally substituted (hetero) aryl group comprising from 5 to 7 members, preferably the optionally substituted benzo group; > Q 'represents one or more anionic counter-ions allowing to reach the electro-neutrality of the molecule. 2. Method according to the preceding claim, in which the compound or compounds of formula (I) are as taken together or separately: > ALK represents a divalent, linear or branched, saturated hydrocarbon chain comprising from 1 to 18 carbon atoms, unsubstituted; > p is 1, 2 or 3, preferably 1; > L represents a group - (CH = CH-) _t -, and t is 1, or 2, preferably t is 1; or> A represents a (hetero) aryl group optionally substituted by one or more atoms or groups chosen from: o C1-C6 linear or branched alkyl, optionally substituted by one or more atoms or groups chosen from: hydroxy -OH, (Ci-C4) alkoxy, amino -N (R) -R ', with R and R' identical or different, being as defined in claim 1, o -N (R) -R ', R and R ', identical or different, being as defined in claim 1, -OR o, R representing a hydrogen atom, an alkyl group-alkyl, preferably Ci-C _4, linear or branched, and o -CN; and / or> Ra, Rb Rc and Rd _; identical or different, represent a hydrogen atom, a group (Ci-C6alkyl, and / or two contiguous groups R _a and Rb, form together with the carbon atom which carry them a benzo group. 3. Method according to any one of the preceding claims, in which the compound or compounds of formula (I) are chosen from those of formula (la) and (Ib) as well as their tautomeric forms, optical isomers, geometric isomers, their salts. addition with an acid or a base, organic or mineral, and / or their solvates; Formulas (la) and (Ib) in which: > n represents an integer ranging from 1 to 12; > Ri, R ₂ , R3, R4 and R5 represent independently of each other: o a hydrogen atom, o a C1-C6 alkyl group, linear or branched, optionally substituted by: -OH, -N (R) -R ', R and R' representing a hydrogen atom, a C1-C4 alkyl group, linear or branched, optionally substituted by -OH, o -N (R) (R ' ), R and R 'being as defined above, o -OR, R representing a hydrogen atom, a C1-C6, preferably C1-C4 alkyl group, linear or branched, o a halogen atom, or o -CN; and> R _a and Rb represent a hydrogen atom, or R _a and R _b form together with the carbon atoms which carry them, a benzo group: 4. Method according to the preceding claim, in which the compounds of formula (la) or (Ib) are such that, taken together or separately: > n represents an integer ranging from 1 to 6, preferably ranging from 1 to 4; > Ri, R ₂ , R3, R4 and R5 represent independently of each other: o a hydrogen atom, o a C1-C4, preferably C1-C4 alkyl group, linear or branched, optionally substituted by: -OH, -N (R) -R ', R and R' having the same meanings as in claim 1 or 3, o -N (R) -R ', R and R' having the same meanings as above , or o -OR, R having the same meanings as above; and / or> R _a and Rb a hydrogen atom, or R _a and Rb form, with the carbon atoms which carry them, a benzo ring. 5. Method according to any one of claims 3 or 4 in which the compounds of formula (la) or (Ib) are such that, taken together or separately: > n represents an integer ranging from 1 to 4, such as 1 or 2; > Ri, R2, R3, R4 and R5 represent independently of each other: o a hydrogen atom, o -N (R) -R ', R and R' representing a hydrogen atom, a C1-C4 alkyl group, linear or branched, optionally substituted by -OH, o -OR, R representing a C1-C6, preferably C1-C4 alkyl group, linear or branched; and / or> R _a and Rb represent a hydrogen atom. 6. Method according to any one of claims 3 to 5, in which the compounds of formula (la) or (Ib) are such that, taken together or separately: • n is 1, • Ri, R2, R3, R4 and R5 represent independently of each other: o a hydrogen atom, or o -OR, R representing a hydrogen atom, a C1-C4 alkyl group, linear or branched, and / or> R _a and Rb represent a hydrogen atom. 7. Method according to any one of the preceding claims, in which the compounds of formula (I), (la) or (Ib) are chosen 5 among: OH with Q 'as defined in claim 1, preferably Q represents 4-CH ₃ -phenyl-SO3'. 8. Method according to any one of the preceding claims, for coloring light keratin materials in which the cosmetic composition is applied to keratin materials, more particularly light keratin fibers preferably with a tone height greater than 6 (HT> 6). 9. Method according to any one of claims 1 to 7, for coloring and lightening dark keratin materials in which the cosmetic composition is applied to dark keratin materials, preferably keratin fibers of HT tone height less than or equal to 6, more preferably less than or equal to 4, such as 2. 10. Method according to any one of the preceding claims, not using a reducing agent. 11. Method according to any one of the preceding claims not using a chemical oxidizing agent. 12. Cosmetic composition which comprises one or more compounds chosen from those of formula (I), (la) and (Ib) as defined in any one of claims 1 to 7. 13. Composition according to the preceding claim, in which the compound or compounds of formula (I), (la) and / or (Ib) represent from 0.001 to 10% by weight, more particularly from 0.005 to 6% by weight relative to the total weight of the composition. 14. Composition according to any one of claims 12 or 13 which does not contain a chemical oxidizing agent. 15. Compound chosen from those of formula (la) and (Ib) as defined in any one of claims 3 to 7. 16. Process for the preparation of the compounds of formula (la) and (Ib) as defined in any one of claims 3 to 7, according to the following synthetic schemes 2 and 3: > Diagram 2: scheme 2 in which R _a , Rb, Ri, R2, R3, R4, R5 and n are as defined in claims 3 to 7, and X represents an oxygen or sulfur atom; process according to diagram 2 which includes: a first step i) in which the alcohol carbonate is functionalized by a leaving group of the tosyl type by the action of thionyl halide such as the chloride of paratoluenesulfonic acid, preferably in a solvent of the aprotic type, which can be apolar, in particular halogenated, such as dichloromethane or polar, such as tetrahydrofuran (THF), in the presence of a preferably organic tertiary base such as triethylamine or N, Ndiisopropylethylamine, at a temperature between 0 and 5 ° C; - a second step ii), in which the carbonate derivative thus functionalized (! ') is then reacted with at least one equivalent of the 4-methylpyridine compound substituted with R _a and Rb, preferably heated to a temperature between 60 ° C and 100 ° C, or at solvent reflux to yield the compound (2 '); - a third step iii), in which the compound (2 ’) is placed 5 reaction, with an equivalent of (thio) aldehyde in a protic solvent such as, methanol or ethanol, in the presence of at least one equivalent of an organic base preferably chosen from pyrrolidine acetate or a tertiary base such as triethylamine or Ν, Ν-diisopropylamine, preferably at a temperature between 10 30 ° C and 100 ° C to lead to the obtaining of the compound (a) belonging to the general formula (la); > Scheme 3 scheme 3 in which R _a , Rb, Ri, R2, R3, R4, R5, X and n being as defined above, Ri and R'i; identical or different, representing a (Ci-Ce) alkyl, arylalkyl group such as benzyl or aryl, and Hal, and Hal ', identical or different, represent a halogen atom, preferably chlorine. ; process according to diagram 3 which includes: a first step i) in which the pyridine 4-haloalkyl (4) is reacted in a polar solvent, preferably aprotic, such as THF, in the presence of a hydride such as, for example, sodium hydride , preferably at low temperature ie at a temperature between -5 ° C and 5 ° C in the presence of a phosphonic acid diester, such as diethyl phosphonate; a second step ii), in which the phosphonate compound (5) thus obtained is reacted in a polar solvent, preferably aprotic, such as tetrahydrofuran, in the presence of a hydride such as sodium hydride, and an aldehyde equivalent at a temperature between 5 ° C and 60 ° C; and a third step iii) in which the compound (6) is reacted with the carbonate derivative (1 ′) previously prepared, in a polar protic solvent such as, for example, methanol, ethanol or isopropanol, at a temperature between 30 ° C and 110 ° C to lead to the compound of the compound (I'b) belonging to the general formula (Ib) being obtained; it being understood that the compounds (a) and (I’b) can then be purified by conventional purification methods such as by chromatography and / or recrystallization. 17. Use of one or more compounds chosen from those of formula (I), (la) and (Ib) as defined in any one of claims 1 to 7, for the coloring and / or lightening of keratin materials, in particular keratin fibers, in particular human fibers such as the hair. 18. Use according to the preceding claim for the coloring and lightening of dark keratin materials, in particular dark keratin fibers, in particular keratin fibers with a pitch less than or equal to 6, preferably less than or equal to 4. 19. Use according to claim 17 or 18 of one or more compounds chosen from those of formula (I), (la) and (Ib) as defined in any one of claims 1 to 7, in the absence of agent chemical oxidant and / or in the absence of reducing agent.