# US 7,410,506 B2 · Dicationic bis-hydrazone compound, dye composition comprising at least one such compound, implementation process therefor and uses thereof

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- Number: US 7,410,506 B2
- Document ID: US7410506B2
- Status: Granted
- Kind: B2
- Application number: 11/249,370
- Filed: 2005-10-14
- Published: 2006-05-11
- Granted: 2008-08-12
- Earliest claimed: 2004-10-14
- Assignees: L'oreal
- Inventors: Hervé David; Andrew Greaves; Leïla Hercouet; Alain Lagrange
- Web page: https://patentgrep.com/patent/US7410506B2

## CPC

- A61K 8/4946: {Imidazoles or their condensed derivatives, e.g. benzimidazoles}
- A61K 8/494: {with more than one nitrogen as the only hetero atom}
- A61Q 5/065: {Preparations for temporary colouring the hair, e.g. direct dyes}
- A61Q 5/10: Preparations for permanently dyeing the hair
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS

## Abstract

The present disclosure relates to a novel family of dicationic bis-hydrazone compounds that may be used as direct dyes, and to a dye composition for dyeing keratin fibers, for example, human keratin fibers such as the hair, comprising, in a suitable dyeing medium, at least one such compound. Also disclosed are dyeing processes implementing this composition and uses thereof.

## Claims

### Claim 1

A dicationic bis-hydrazone compound of formula (I)
DYE-L-DYE
in which each of the chromophores DYE, which may be identical or different, is chosen from chromophores of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) below:
wherein:
the groups R1 and R5, independently of each other, are chosen from linear or branched, saturated or unsaturated C1-C20 hydrocarbon-based chains, which can form one or more optionally substituted, optionally aromatic 3- to 7-membered carbon-based rings, the chains being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom,
the groups R2 and R3, independently of each other, are chosen from:
a halogen atom chosen from bromine, chlorine and fluorine;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form one or more optionally aromatic 3- to 6-membered carbon-based rings, the chain being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
a hydroxyl group;
a C1-C4 alkoxy group; a C2-C4 (poly)hydroxyalkoxy group; an alkoxycarbonyl group (RO—CO—) in which R is a C1-C4 alkyl radical; or an alkylcarbonyloxy radical (RCO—O—) in which R is a C1-C4 alkyl radical; an optionally substituted aryloxy group;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a carbamoyl group ((R)2N—CO—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a sulfonamide group ((R)2N—SO2—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylthio group (R—S—) in which the group R is a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
a nitro group; a cyano group; a halogen atom;
a trifluoromethyl group (CF3);
R1 and R2 may also form, with the nitrogen atom substituted with R1, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered heterocycle;
two adjacent radicals R2 may form, together with the carbon atoms to which they are attached, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
two adjacent radicals R3 can together form a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
the groups R4, independently of each other, are chosen from:
a hydrogen atom;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form at least one optionally aromatic 3- to 6-membered carbon-based ring, the chains being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
n is an integer from 0 to 5,
n′ is an integer from 0 to 4,
the bond a in formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) links each of the chromophores DYE to the linker L of formula (I),
X is an organic or mineral anion or mixture of anions for equilibrating the charge(s) of the compound Ia or Ib;
the group L is a linear or branched C1-C60 hydrocarbon-based chain that can form at least one optionally aromatic, optionally substituted 3- to 7-membered carbon-based ring, the chain being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom, L not comprising any peroxide, nitro, diazo or nitroso groups, the linker L being linked to the quaternized nitrogen atom of each of the chromophores DYE via a carbon atom, L not being cationic;
with the proviso that when the two chromophores DYE are identical and correspond to formula (Ia) with n=n′=0, then the group L is not one of the following groups:

### Claim 2 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein in formula (I), L is chosen from alkylene radicals (CnH2n) comprising from 1 to 60 carbon atoms, optionally substituted and/or interrupted with at least one hetero atom.

### Claim 3 (depends on 2)

A dicationic bis-hydrazone compound according to claim 2, wherein L is chosen from alkylene radicals (CnH2n) comprising from 2 to 20 carbon atoms, optionally substituted and/or interrupted with at least one hetero atom.

### Claim 4 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein L is C1-C20 alkyl-(hetero)aryl-C1-C20 alkyl.

### Claim 5 (depends on 4)

A dicationic bis-hydrazone compound according to claim 4, wherein L is C1-C10 alkyl-(hetero)aryl-C1-C10 alkyl.

### Claim 6 (depends on 1)

A dicationic bis-hydrazone compound according claim 1, wherein the groups R1 are identical and are chosen from C1-C4 alkyl radicals optionally substituted with at least one radical chosen from hydroxyl, C1-C2 alkoxy, amino and C1-C2 (di)alkylamino radicals; an alkylcarbonyl radical (R—CO—) in which the radical R is a C1-C4 alkyl radical; a carbamoyl group ((R)2N—CO—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylsulfonyl radical (R—SO2—) in which the radical R is a C1-C4 alkyl radical.

### Claim 7 (depends on 6)

A dicationic bis-hydrazone compound according to claim 6, wherein the groups R1 are identical and are chosen from methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl, acetyl (CH3CO—) and methylsulfonyl (CH3SO2—) radicals.

### Claim 8 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein the groups R1 and R2 form, with the nitrogen atom substituted with R1, a saturated or unsaturated 5- or 6-membered heterocycle substituted with at least one alkyl radical.

### Claim 9 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein the groups R2 and R3 are chosen from, independently of each other:
a hydrogen atom;
a halogen atom;
linear or branched C1-C4 alkyl radicals optionally substituted with at least one radical chosen from hydroxyl, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amino, C1-C2 (di)alkylamino, thio (—SH), (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyle and (C1-C4)thioalkyl radicals;
phenyl radicals optionally substituted with at least one radical chosen from hydroxyl, C1-C2 alkoxy, C2-C4(poly)hydroxyalkoxy, amino and C1-C2(di)alkylamino radicals, or a halogen atom chosen from chlorine, fluorine and bromine;
C1-C4 alkoxy radicals;
(C1-C4)alkylsulfonylamino radicals;
C2-C4 (poly)hydroxyalkoxy radicals;
amino radicals;
C1-C2 (di)alkylamino radicals;
C2-C4 (poly)hydroxyalkylamino radicals;
alkylcarbonyl radicals (R—CO—) in which the radical R is a C1-C4 alkyl radical;
carbamoyl radicals ((R)2N—CO—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
alkylsulfonylamino radicals (RSO2N—) in which the radical R is a C1-C4 alkyl radical;
aminosulfonyl radicals ((R)2NSO2—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
alkylthio radicals (RS—) in which the radical R is a C1-C4 alkyl radical;
thio radicals (HS—)
alkylsulfinyl radicals (RSO—) in which the radical R is a C1-C4 alkyl radical;
alkylsulfonyl radicals (R—SO2—) in which the radical R is a C1-C4 alkyl radical;
alkylcarbonylamino radicals (RCONR′—) in which the radical R is chosen from a hydrogen atom and a C1-C4 alkyl radical and the radical R′ is chosen from a hydrogen atom and a C1-C4 alkyl radical.

### Claim 10 (depends on 9)

A dicationic bis-hydrazone compound according to claim 9, wherein the groups R2 and R3 are chosen from, independently of each other, a hydrogen atom and methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl, acetyl (CH3CO—), methylsulfonyl (CH3SO2—), amide (CH3CONH—), hydroxyl, amino, methylamino, dimethylamino, 2-hydroxyethylamino, methoxy, ethoxy and phenyl radicals.

### Claim 11 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein the groups R5 are identical and are chosen from C1-C4, alkyl radicals optionally substituted with at least one radical chosen from hydroxyl, C1-C2 alkoxy, amino and C1-C2 (di)alkylamino radicals; and an optionally substituted phenyl radical.

### Claim 12 (depends on 11)

A dicationic bis-hydrazone compound according to claim 11, wherein the groups R5 are identical and are chosen from methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl and phenyl radicals.

### Claim 13 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein said compound is chosen from the compounds of formulae:
in which:
R′, which may be identical or different, have the same definition as R2 of claim 1,
R″, which may be identical or different, are chosen from a hydrogen atom and a C1-C4 alkyl radical,
m is an integer from 2 to 6,
n″ is an integer from 0 to 4.

### Claim 14 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein said compound is chosen from the compounds of formulae:
in which:
R′, which may be identical or different, have the same definition as R2 of claim 1,
R″, which may be identical or different, are chosen from a hydrogen atom and a C1-C4 alkyl radical,
m is an integer from 2 to 6,
n″ is an integer from 0 to 4.

### Claim 15 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein said compound is chosen from the compounds of formulae:
in which the radicals R1, R2, R3, R4, R5, X, n, n′and L are as defined in claim 1.

### Claim 16 (depends on 1)

A dicationic bis-hydrazone compound according to claim 1, wherein the compound is chosen from the following compounds:
4-{(E)-[methyl(phenyl)hydrazono]methyl}-1-[3-(4-{(E)-[methyl(phenyl)hydrazono]methyl}pyridinium-1-yl)propyl]pyridinium dibromide,
4-{(E)-[methyl(phenyl)hydrazono]methyl}-1-[4-(4-((E)-[methyl(phenyl)hydrazono]methyl}pyridinium-1-yl)butyl]pyridinium dibromide
4-{(E)-[methyl(phenyl)hydrazono]methyl}-1-[5-(4-{(E)-[methyl(phenyl)hydrazono]methyl}pyridinium-1-yl)pentyl]pyridinium dibromide
4-{(E)-[methyl(phenyl)hydrazono]methyl}-1-[6-(4-{(E)-[methyl(phenyl)hydrazono]methyl}pyridinium-1-yl)hexyl]pyridinium dibromide
4-{(E)-[methyl(phenyl)hydrazono]methyl}-1-(6-{[4-({[6-(4-{(E)-[methyl(phenyl)hydrazono]methyl}pyridinium-1-yl)hexyl]amino}carbonyl)benzoyl]amino}hexyl)pyridinium dibromide
4-{(E)-[methyl(phenyl)hydrazono]methyl}-1-[6-(4-{(E)-[methyl(phenyl)hydrazono]methyl}quinolinium-1-yl)hexyl]quinolinium dibromide
4-{(E)-[methyl(phenyl)hydrazono]methyl}-1-[6-(4-{(E)-[methyl(phenyl)hydrazono]methyl}pyridinium-1-yl)hexyl]quinolinium dibromide
1-methyl-3-[5-(1-methyl-2-{(E)-[methyl(phenyl)hydrazono]methyl}-1H-imidazol-3-ium-3-yl)pentyl]-2-{(E)-[methyl(phenyl)hydrazono]methyl}-1H-imidazol-3-ium dibromide
1-methyl-3-[4-(1-methyl-2-{(E)-[methyl(phenyl)hydrazono]methyl}-1H-benzimidazol-3-ium-3-yl)butyl]-2-{(E)-[methyl(phenyl)hydrazono]methyl}-1H-benzimidazol-3-ium dibromide
1-[6-(1-methyl-2-{(E)-[methyl(phenyl)hydrazono]methyl}-1H-imidazol-3-ium-3-yl)hexyl]-4-{(E)-[methyl(phenyl)hydrazono]methyl}quinolinium dibromide
1-[6-(1-methyl-2-{(E)-[methyl(phenyl)hydrazono]methyl}-1H-benzimidazol-3-ium-3-yl)hexyl]-4-{(E)-[methyl(phenyl)hydrazono]methyl}quinolinium dibromide,
1,1′-pentane-1,5-diylbis(4-{(E)-[methyl(phenyl)hydrazono]methyl}quinolinium) dibromide,
1,1′-butane-1,4-diylbis(4-{(E)[methyl(phenyl)hydrazono]methyl}quinolinium) dibromide,
1,1′-propane-1,3-diylbis(4-{(E)-[methyl(phenyl)hydrazono]methyl}quinolinium) dibromide,
2-{(E)-[{4-[(4-methoxyphenyl)(methyl)amino]phenyl}(methyl)hydrazono]methyl}-3,3-dimethyl-1-[6-(4{(E)-[methyl(phenyl)hydrazono]methyl}pyridinium-1-yl)hexyl]-3H-indolium dichloride,
1,1′-hexane-1,6-diylbis(2-{(E)-[{4-[(4-methoxyphenyl)(methyl)amino]phenyl}(methyl)hydrazono]methyl}-3,3-dimethyl-3H-indolium) dichloride.

### Claim 17

A dye composition for dyeing keratin fibers, comprising, in a suitable dyeing medium, at least one dicationic bis-hydrazone compound of formula (I)
DYE-L-DYE
in which each of the chromophores DYE, which may be identical or different, is chosen from chromophores of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) below:
wherein:
the groups R1 and R5, independently of each other, are chosen from linear or branched, saturated or unsaturated C1-C20 hydrocarbon-based chains, which can form one or more optionally substituted, optionally aromatic 3- to 7-membered carbon-based rings, the chains being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom,
the groups R2 and R3, independently of each other, are chosen from:
a halogen atom chosen from bromine, chlorine and fluorine;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form one or more optionally aromatic 3- to 6-membered carbon-based rings, the chain being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
a hydroxyl group;
a C1-C4 alkoxy group; a C2-C4 (poly)hydroxyalkoxy group; an alkoxycarbonyl group (RO—CO—) in which R is a C1-C4 alkyl radical; or an alkylcarbonyloxy radical (RCO—O—) in which R is a C1-C4 alkyl radical; an optionally substituted aryloxy group;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a carbamoyl group ((R)2N—CO—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a sulfonamide group ((R)2N—SO2—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylthio group (R—S—) in which the group R is a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
a nitro group; a cyano group; a halogen atom;
a trifluoromethyl group (CF3);
R1 and R2 may also form, with the nitrogen atom substituted with R1, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered heterocycle;
two adjacent radicals R2 may form, together with the carbon atoms to which they are attached, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
two adjacent radicals R3 can together form a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
the groups R4, independently of each other, are chosen from:
a hydrogen atom;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form at least one optionally aromatic 3- to 6-membered carbon-based ring, the chains being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
n is an integer from 0 to 5,
n′ is an integer from 0 to 4,
the bond a in formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) links each of the chromophores DYE to the linker L of formula (I),
X is an organic or mineral anion or mixture of anions for equilibrating the charge(s) of the compound Ia or Ib;
the group L is a linear or branched C1-C60 hydrocarbon-based chain that can form at least one optionally aromatic, optionally substituted 3- to 7-membered carbon-based ring, the chain being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom, L not comprising any peroxide, nitro, diazo or nitroso groups, the linker L being linked to the quaternized nitrogen atom of each of the chromophores DYE via a carbon atom, L not being cationic;
with the proviso that when the two chromophores DYE are identical and correspond to formula (Ia) with n=n′=0, then the group L is not one of the following groups:

### Claim 18 (depends on 17)

A dye composition according to claim 17, wherein said at least one dicationic bis-hydrazone compound is present in an amount ranging from 0.001 to 10% by weight relative to the total weight of the composition.

### Claim 19 (depends on 18)

A dye composition according to claim 18, wherein said at least one dicationic bis-hydrazone compound is present in an amount ranging from 0.01 to 10% by weight relative to the total weight of the composition.

### Claim 20 (depends on 17)

A dye composition according to claim 17, further comprising at least one additional direct dye.

### Claim 21 (depends on 17)

A dye composition according to claim 17, further comprising at least one oxidation dye precursor chosen from oxidation bases and couplers.

### Claim 22 (depends on 21)

A dye composition according to claim 21, wherein said at least one oxidation base is chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.

### Claim 23 (depends on 21)

A dye composition according to claim 21, wherein the at least one oxidation base is present in an amount ranging from 0.001% to 20% by weight relative to the total weight of the composition.

### Claim 24 (depends on 23)

A dye composition according to claim 23, wherein the at least one oxidation base is present in an amount ranging from 0.005% to 6% by weight relative to the total weight of the composition.

### Claim 25 (depends on 21)

A dye composition according to claim 21, further comprising at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.

### Claim 26 (depends on 25)

A dye composition according to claim 25, wherein the at least one coupler is present in an amount ranging from 0.001% to 20% relative to the total weight of the composition.

### Claim 27 (depends on 26)

A dye composition according to claim 26, wherein the at least one coupler is present in an amount ranging from 0.005% to 6% by weight relative to the total weight of the composition.

### Claim 28 (depends on 17)

A dye composition according to claim 17, further comprising at least one hydroxylated solvent.

### Claim 29 (depends on 28)

A dye composition according to claim 28, wherein said at least one hydroxylated solvent is chosen from ethanol, propylene glycol, glycerol and polyol monoethers.

### Claim 30 (depends on 17)

A dye composition according to claim 17, further comprising at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersants, conditioning agents, film-forming agents, ceramides, preserving agents and opacifiers.

### Claim 31 (depends on 17)

A dye composition according to claim 17, further comprising at least one oxidizing agent chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.

### Claim 32

A process for dyeing keratin fibers, comprising applying a dye composition to keratin fibers and leaving it to act for a period sufficient to obtain a desired coloration, wherein said dye composition comprises, in a suitable dyeing medium, at least one dicationic bis-hydrazone compound of formula (I)
DYE-L-DYE
in which each of the chromophores DYE, which may be identical or different, is chosen from chromophores of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) below:
wherein:
the groups R1 and R5, independently of each other, are chosen from linear or branched, saturated or unsaturated C1-C20 hydrocarbon-based chains, which can form one or more optionally substituted, optionally aromatic 3- to 7-membered carbon-based rings, the chains being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom,
the groups R2 and R3, independently of each other, are chosen from:
a halogen atom chosen from bromine, chlorine and fluorine;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form one or more optionally aromatic 3- to 6-membered carbon-based rings, the chain being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
a hydroxyl group;
a C1-C4 alkoxy group; a C2-C4 (poly)hydroxyalkoxy group; an alkoxycarbonyl group (RO—CO—) in which R is a C1-C4 alkyl radical; or an alkylcarbonyloxy radical (RCO—O—) in which R is a C1-C4 alkyl radical; an optionally substituted aryloxy group;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a carbamoyl group ((R)2N—CO—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a sulfonamide group ((R)2N—SO2—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylthio group (R—S—) in which the group R is a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
a nitro group; a cyano group; a halogen atom;
a trifluoromethyl group (CF3);
R1 and R2 may also form, with the nitrogen atom substituted with R1, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered heterocycle;
two adjacent radicals R2 may form, together with the carbon atoms to which they are attached, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
two adjacent radicals R3 can together form a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
the groups R4, independently of each other, are chosen from:
a hydrogen atom;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form at least one optionally aromatic 3- to 6-membered carbon-based ring, the chains being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
n is an integer from 0 to 5,
n′ is an integer from 0 to 4,
the bond a in formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) links each of the chromophores DYE to the linker L of formula (I),
X is an organic or mineral anion or mixture of anions for equilibrating the charge(s) of the compound Ia or Ib;
the group L is a linear or branched C1-C60 hydrocarbon-based chain that can form at least one optionally aromatic, optionally substituted 3- to 7-membered carbon-based ring, the chain being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom, L not comprising any peroxide, nitro, diazo or nitroso groups, the linker L being linked to the quaternized nitrogen atom of each of the chromophores DYE via a carbon atom, L not being cationic;
with the proviso that when the two chromophores DYE are identical and correspond to formula (Ia) with n=n′=0, then the group L is not one of the following groups:

### Claim 33

A process for obtaining dyeing results on keratin fibers that show good resistance to external agents and to shampoo, said process comprising applying to keratin fibers a dye composition comprising, in a suitable dyeing medium, at least one dicationic bis-hydrazone compound of formula (I)
DYE-L-DYE
in which each of the chromophores DYE, which may be identical or different, is chosen from chromophores of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) below:
wherein:
the groups R1 and R5, independently of each other, are chosen from linear or branched, saturated or unsaturated C1-C20 hydrocarbon-based chains, which can form one or more optionally substituted, optionally aromatic 3- to 7-membered carbon-based rings, the chains being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom,
the groups R2 and R3, independently of each other, are chosen from:
a halogen atom chosen from bromine, chlorine and fluorine;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form one or more optionally aromatic 3- to 6-membered carbon-based rings, the chain being optionally substituted or being optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
a hydroxyl group;
a C1-C4 alkoxy group; a C2-C4 (poly)hydroxyalkoxy group; an alkoxycarbonyl group (RO—CO—) in which R is a C1-C4 alkyl radical; or an alkylcarbonyloxy radical (RCO—O—) in which R is a C1-C4 alkyl radical; an optionally substituted aryloxy group;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a carbamoyl group ((R)2N—CO—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; a sulfonamide group ((R)2N—SO2—) in which the radicals R, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylthio group (R—S—) in which the group R is a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
a nitro group; a cyano group; a halogen atom;
a trifluoromethyl group (CF3);
R1 and R2 may also form, with the nitrogen atom substituted with R1, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered heterocycle;
two adjacent radicals R2 may form, together with the carbon atoms to which they are attached, a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
two adjacent radicals R3 can together form a saturated or unsaturated, substituted or unsubstituted 5- or 6-membered aromatic ring or heterocycle;
the groups R4, independently of each other, are chosen from:
a hydrogen atom;
linear or branched, saturated or unsaturated C1-C16 hydrocarbon-based chains, which can form at least one optionally aromatic 3- to 6-membered carbon-based ring, the chains being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing at least one hetero atom;
an amino group, an amino group substituted with at least one C1-C4 alkyl radical, which may be identical or different, optionally bearing at least one hydroxyl group, the two alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 6-membered heterocycle, optionally bearing another nitrogen or non-nitrogen hetero atom; an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, are chosen from C1-C4 alkyl radicals; a ureido group (N(R)2—CO—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical; an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, are chosen from a hydrogen atom and a C1-C4 alkyl radical;
n is an integer from 0 to 5,
n′ is an integer from 0 to 4,
the bond a in formulae (Ia), (Ib), (Ic), (Id), (Ie), (If) and (Ig) links each of the chromophores DYE to the linker L of formula (I),
X is an organic or mineral anion or mixture of anions for equilibrating the charge(s) of the compound Ia or Ib;
the group L is a linear or branched C1-C60 hydrocarbon-based chain that can form at least one optionally aromatic, optionally substituted 3- to 7-membered carbon-based ring, the chain being optionally substituted, optionally interrupted with at least one hetero atom or with at least one group bearing a hetero atom, L not comprising any peroxide, nitro, diazo or nitroso groups, the linker L being linked to the quaternized nitrogen atom of each of the chromophores DYE via a carbon atom, L not being cationic;
with the proviso that when the two chromophores DYE are identical and correspond to formula (Ia) with n=n′=0, then the group L is not one of the following groups: