Cationic aminoanthraquinones, their use for dyeing keratinous fibers, dyeing compositions containing them and methods of dyeing

A dyeing composition for keratinous materials comprising, in a medium appropriate for dyeing, at least one cationic aminoanthraquinone of formula (I) or an acid addition salt thereof, present in an amount effective for dyeing said keratinous materials:

• in which:
• R1, R2, R3 and R4, which may be identical or different, are chosen from a hydrogen atom;
• a halogen atom;
• a group Z defined below;
• a (C1-C6)alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano radical;
• a nitro radical;
• a carboxyl radical;
• a carbamyl radical;
• a sulpho radical;
• an unsubstituted amino radical;
• a substituted amino radical NHR′5, wherein R′5 has the same definition as R5 below, and wherein R′5 may be identical to or different from R5 below;
• and an OR6 and SR6 group, wherein R6 is as defined below;
• R5 is chosen from a hydrogen atom;
• a group Z defined below;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a thiocarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a sulpho(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, carbamyl, N-(C1-C6)alkylcarbamyl, N,N-di(C1-C6)alkylcarbamyl, (C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, thiocarbamyl, and a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms;
• R6 is chosen from a hydrogen atom;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a group Z defined below;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, N-(C1-C6)alkylcarbamyl, N, N-di(C1-C6)alkylcarbamyl, thiocarbamyl, and (C1-C6)alkylsulphonyl radicals, and from a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms
• Z is chosen from the unsaturated cationic groups of formulae (II) and (III), and the saturated cationic groups of formula (IV):
• in which:
• D is a linking arm which is chosen from linear and branched alkyl chains, which may be interrupted by at least one heteratom, and which may be substituted with at least one radical chosen from a hydroxyl and a C1-C6 alkoxy, and which may carry at least one ketone function;
• E, G, J, L and M, which are identical or different, are chosen from carbon, oxygen, sulphur, and nitrogen atoms;
• n is an integer ranging from 0 to 4;
• m is an integer ranging from 0 to 5;
• the radicals R, which are identical or different, are chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• a halogen atom;
• a hydroxyl radical;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a nitro radical;
• a cyano radical;
• a cyano(C1-C6 alkyl) radical;
• a C1-C6 alkoxy radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• an amido radical;
• an aldehydo radical;
• a carboxyl radical;
• a C1-C6 alkylcarbonyl radical;
• a thio radical;
• a thio(C1-C6 alkyl) radical;
• a (C1-C6)alkylthio radical;
• an amino radical;
• an amino radical protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• and an NHR″ and an NR″R′″ group, wherein R″ and R′″, which are identical or different, are chosen from a C1-C6 alkyl radical, a monohydroxy(C1-C6 alkyl) radical, and a polyhydroxy(C2-C6 alkyl) radical;
• R7 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a benzyl radical;
• and a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R8, R9 and R10, which are identical or different, are chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amido(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• and an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• two of the radicals R8, R9 and R10 may also form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring containing atoms selected from carbon and heteroatoms;
• one of the radicals R8, R9 and R10 may also be chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R11 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amino(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and a (C1-C6)alkylsulphonyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a sulphonamido(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylketo(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• and an N-(C1-C6)alkylsulphonamido(C1-C6 alkyl) radical;
• x and y are integers equal to 0 or 1, with the following conditions:
• in the unsaturated cationic groups of formula (II):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J or L;
• y may only be 1:
• 1) when F, G, J and L are simultaneously a carbon atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• or
• 2) when at least one of E, G, J and L is a nitrogen atom onto which the radical R7 is attached;
• in the unsaturated cationic groups of formula (III):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J, L or M;
• y may only take the value 1 when at least one of E, G, J, L and M is a divalent atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• in the cationic groups of formula (IV):
• when x is 0, then the linking arm D is attached to the nitrogen atom carrying the radicals R8 to R10;
• when x is 1, then two of the radicals R8 to R10 conjointly form, with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring as defined above and the linking arm D is carried by a carbon atom of the saturated ring;
• X−1 is chosen from monovalent and divalent anions;
• it being understood that:
• the number of unsaturated cationic groups Z of formula (II), in which at least one of E, G, J and L is a nitrogen atom is at least equal to 1.

A direct dyeing composition for keratinous materials comprising, in a medium appropriate for dyeing, at least one cationic aminoanthraquinone of formula (I) or an acid addition salt thereof, present in an amount effective for dyeing said keratinous materials:

• in which:
• R1, R2, R3 and R4, which may be identical or different, are chosen from a hydrogen atom;
• a halogen atom;
• a group Z defined below;
• a (C1-C6)alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano radical;
• a nitro radical;
• a carboxyl radical;
• a carbamyl radical;
• a sulpho radical;
• an unsubstituted amino radical;
• a substituted amino radical NHR′5, wherein R′5 has the same definition as R5 below, and wherein R′5 may be identical to or different from R5 below;
• and an OR6 and SR6 group, wherein R6 is as defined below;
• R5 is chosen from a hydrogen atom;
• a group Z defined below;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a thiocarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a sulpho(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, carbamyl, N-(C1-C6)alkylcarbamyl, N,N-di(C1-C6)alkylcarbamyl, (C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, thiocarbamyl, and a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms;
• R6 is chosen from a hydrogen atom;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a group Z defined below;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, N-(C1-C6)alkylcarbamyl, N,N-di(C1-C6)alkylcarbamyl, thiocarbamyl, and (C1-C6)alkylsulphonyl radicals, and from a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms
• Z is chosen from the unsaturated cationic groups of formulae (II) and (III), and the saturated cationic groups of formula (IV):
• in which:
• D is a linking arm which is chosen from linear and branched alkyl chains, which may be interrupted by at least one heteratom, and which may be substituted with at least one radical chosen from a hydroxyl and a C1-C6 alkoxy, and which may carry at least one ketone function;
• E, G, J, L and M, which are identical or different, are chosen from carbon, oxygen, sulphur, and nitrogen atoms;
• n is an integer ranging from 0 to 4;
• m is an integer ranging from 0 to 5;
• the radicals R, which are identical or different, are chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• a halogen atom;
• a hydroxyl radical;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a nitro radical;
• a cyano radical;
• a cyano(C1-C6 alkyl) radical;
• a C1-C6 alkoxy radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• an amido radical;
• an aldehydo radical;
• a carboxyl radical;
• a C1-C6 alkylcarbonyl radical;
• a thio radical;
• a thio(C1-C6 alkyl) radical;
• a (C1-C6)alkylthio radical;
• an amino radical;
• an amino radical protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• and an NHR″ and an NR″R″ group, wherein R″ and R′″, which are identical or different, are chosen from a C1-C6 alkyl radical, a monohydroxy(C1-C6 alkyl) radical, and a polyhydroxy(C2-C6 alkyl) radical;
• R7 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a benzyl radical;
• and a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R8, R9 and R10, which are identical or different, are chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amido(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• and an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-Cs)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• two of the radicals R8, R9 and R10 may also form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring containing atoms selected from carbon and heteroatoms;
• one of the radicals R8, R9 and R10 may also be chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R11 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amino(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and a (C1-C6)alkylsulphonyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a sulphonamido(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylketo(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• and an N-(C1-C6)alkylsulphonamido(C1-C6 alkyl) radical;
• x and y are integers equal to 0 or 1, with the following conditions:
• in the unsaturated cationic groups of formula (II):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J or L;
• y may only be 1:
• 1) when E, G, J and L are simultaneously a carbon atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• or
• 2) when at least one of F, G, J and L is a nitrogen atom onto which the radical R7 is attached;
• in the unsaturated cationic groups of formula (III):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J, L or M;
• y may only take the value 1 when at least one of E, G, J, L and M is a divalent atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• in the cationic groups of formula (IV):
• when x is 0, then the linking arm D is attached to the nitrogen atom carrying the radicals R8 to R10;
• when x is 1, then two of the radicals R8 to R10 conjointly form, with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring as defined above and the linking arm D is carried by a carbon atom of the saturated ring;
• X− is chosen from monovalent and divalent anions
• it being understood that:
• the number of unsaturated cationic groups Z of formula (II), in which at least one of E, G, J and L is a nitrogen atom is at least equal to 1.

A method of direct dyeing keratinous fibers, said method comprising:

• applying a direct dyeing composition to said fibers, wherein said fibers can be dry or wet, and wherein said direct dyeing composition comprises, in a medium appropriate or dyeing, at least one cationic aminoanthraquinone of formula (I) or an acid addition halt thereof, present in an amount effective for dyeing said keratinous materials;
• and
• drying said fibers without an intermediate step
• wherein said formula (I) is as follows:
• in which:
• R1, R2, R3 and R4, which may be identical or different, are chosen from a hydrogen atom;
• a halogen atom;
• a group Z defined below;
• a (C1-C6)alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano radical;
• a nitro radical;
• a carboxyl radical;
• a carbamyl radical;
• a sulpho radical;
• an unsubstituted amino radical;
• a substituted amino radical NHR′5, wherein R′5 has the same definition as R5 below, and wherein R′5 may be identical to or different from R5 below;
• and an OR6 and SR6 group, wherein R6 is as defined below;
• R5 is chosen from a hydrogen atom;
• a group Z defined below;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a thiocarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a sulpho(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• an N, N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, carbamyl, N-(C1-C6)alkylcarbamyl, N, N-di(C1-C6)alkylcarbamyl, (C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, thiocarbamyl, and a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms;
• R6 is chosen from a hydrogen atom;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a group Z defined below;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, N-(C1-C6)alkylcarbamyl, N, N-di(C1-C6)alkylcarbamyl, thiocarbamyl, and (C1-C6)alkylsulphonyl radicals, and from a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms;
• Z is chosen from the unsaturated cationic groups of formulae (II) and (III), and the saturated cationic groups of formula (IV):
• in which:
• D is a linking arm which is chosen from linear and branched alkyl chains, which may be interrupted by at least one heteratom, and which may be substituted with at least one radical chosen from a hydroxyl and a C1-C6 alkoxy, and which may carry at least one ketone function;
• E, G, J, L and M, which are identical or different, are chosen from carbon, oxygen, sulphur, and nitrogen atoms;
• n is an integer ranging from 0 to 4;
• m is an integer ranging from 0 to 5;
• the radicals R, which are identical or different, are chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• a halogen atom;
• a hydroxyl radical;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a nitro radical;
• a cyano radical;
• a cyano(C1-C6 alkyl) radical;
• a C1-C6 alkoxy radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• an amido radical;
• an aldehydo radical;
• a carboxyl radical;
• a C1-C6 alkylcarbonyl radical;
• a thio radical;
• a thio(C1-C6 alkyl) radical;
• a (C1-C6)alkylthio radical;
• an amino radical;
• an amino radical protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• and an NHR″ and an NR″R″ group, wherein R″ and R′″, which are identical or different, are chosen from a C1-C6 alkyl radical, a monohydroxy(C1-C6 alkyl) radical, and a polyhydroxy(C2-C6 alkyl) radical;
• R7 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a benzyl radical;
• and a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R8, R9 and R10, which are identical or different, are chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amido(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• and an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• two of the radicals R8, R9 and R10 may also form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring containing atoms selected from carbon and heteroatoms;
• one of the radicals R8, R9 and R10 may also be chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R11 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amino(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and a (C1-C6)alkylsulphonyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a sulphonamido(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylketo(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• and an N-(C1-C6)alkylsulphonamido(C1-C6 alkyl) radical;
• x and y are integers equal to 0 or 1, with the following conditions:
• in the unsaturated cationic groups of formula (II):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J or L;
• y may only be 1:
• 1) when E, G, J and L are simultaneously a carbon atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• or
• 2) when at least one of F, G, J and L is a nitrogen atom onto which the radical R7 is attached;
• in the unsaturated cationic groups of formula (III):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J, L or M;
• y may only take the value 1 when at least one of F, G, J, L and M is a divalent atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• in the cationic groups of formula (IV):
• when x is 0, then the linking arm D is attached to the nitrogen atom carrying the radicals R8 to R10;
• when x is 1, then two of the radicals R8 to R10 conjointly form, with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring as defined above and the linking arm D is carried by a carbon atom of the saturated ring;
• X− is chosen from monovalent and divalent anions;
• it being understood that:
• the number of unsaturated cationic groups Z of formula (II), in which at least one of E, G, J and L is a nitrogen atom is at least equal to 1.

A method of direct dyeing keratinous fibers, said method comprising:

• applying a direct dyeing composition to said fibers, wherein said fibers can be wet or dry, and wherein said direct dyeing composition comprises, in a medium appropriate for dyeing, at least one cationic aminoanthraquinone of formula (I) or an acid addition salt thereof, present in an amount effective for dyeing said keratinous materials:
• in which:
• R1, R2, R3 and R4, which may be identical or different, are chosen from a hydrogen atom;
• a halogen atom;
• a group Z defined below;
• a (C1-C6)alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano radical;
• a nitro radical;
• a carboxyl radical;
• a carbamyl radical;
• a sulpho radical;
• an unsubstituted amino radical;
• a substituted amino radical NHR′5, wherein R′5 has the same definition as R5 below, and wherein R′5 may be identical to or different from R5 below;
• and an OR6 and SR6 group, wherein R6 is as defined below;
• R5 is chosen from a hydrogen atom;
• a group Z defined below;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N, N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a thiocarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a sulpho(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, carbamyl, C1-C6)alkylcarbamyl, N, N-di(C1-C6)alkylcarbamyl, (C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, thiocarbamyl, and a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms;
• R6 is chosen from a hydrogen atom;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a group Z defined below;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• an aminosulphonyl(C1-C6 alkyl) radical;
• an N-Z-aminosulphonyl(C1-C6 alkyl) radical;
• an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical;
• an amino(C1-C6 alkyl) radical, wherein the alkyl is substituted with at least one hydroxyl radical and wherein the amine is substituted with one or two radicals, which are identical or different, and which are chosen from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, N-(C1-C6)alkylcarbamyl, N, N-di(C1-C6)alkylcarbamyl, thiocarbamyl, and (C1-C6)alkylsulphonyl radicals, and from a group Z defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing atoms chosen from carbon and heteroatoms;
• Z is chosen from the unsaturated cationic groups of formulae (II) and (III), and the saturated cationic groups of formula (IV):
• in which:
• D is a linking arm which is chosen from linear and branched alkyl chains, which may be interrupted by at least one heteratom, and which may be substituted with at least one radical chosen from a hydroxyl and a C1-C6 alkoxy, and which may carry at least one ketone function;
• E, G, J, L and M, which are identical or different, are chosen from carbon, oxygen, sulphur, and nitrogen atoms;
• n is an integer ranging from 0 to 4;
• m is an integer ranging from 0 to 5;
• the radicals R, which are identical or different, are chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• a halogen atom;
• a hydroxyl radical;
• a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a nitro radical;
• a cyano radical;
• a cyano(C1-C6 alkyl) radical;
• a C1-C6 alkoxy radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• an amido radical;
• an aldehydo radical;
• a carboxyl radical;
• a C1-C6 alkylcarbonyl radical;
• a thio radical;
• a thio(C1-C6 alkyl) radical;
• a (C1-C6)alkylthio radical;
• an amino radical;
• an amino radical protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• and an NHR″ and an NR″R′″ group, wherein R″ and R″, which are identical or different, are chosen from a C1-C6 alkyl radical, a monohydroxy(C1-C6 alkyl) radical, and a polyhydroxy(C2-C6 alkyl) radical;
• R7 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a benzyl radical;
• and a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R8, R9 and R10, which are identical or different, are chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• a (C1-C6)alkoxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amido(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• and an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl;
• two of the radicals R8, R9 and R10 may also form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring containing atoms selected from carbon and heteroatoms;
• one of the radicals R8, R9 and R10 may also be chosen from a group Z′, wherein Z′ has the same definition as Z, and wherein the group Z′ is identical or different from the group Z;
• R11 is chosen from a C1-C6 alkyl radical;
• a monohydroxy(C1-C6 alkyl) radical;
• a polyhydroxy(C2-C6 alkyl) radical;
• an aryl radical;
• a benzyl radical;
• an amino(C1-C6 alkyl) radical;
• an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and a (C1-C6)alkylsulphonyl radical;
• a carboxy(C1-C6 alkyl) radical;
• a cyano(C1-C6 alkyl) radical;
• a carbamyl(C1-C6 alkyl) radical;
• a trifluoro(C1-C6 alkyl) radical;
• a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical;
• a sulphonamido(C1-C6 alkyl) radical;
• a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical;
• a (C1-C6)alkylketo(C1-C6 alkyl) radical;
• an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical;
• and an N-(C1-C6)alkylsulphonamido(C1-C6 alkyl) radical;
• x and y are integers equal to 0 or 1, with the following conditions:
• in the unsaturated cationic groups of formula (II):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J or L;
• y may only be 1:
• 1) when E, G, J and L are simultaneously a carbon atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• or
• 2) when at least one of E, G, J and L is a nitrogen atom onto which the radical R7 is attached;
• in the unsaturated cationic groups of formula (III):
• when x is 0, the linking arm D is attached to the nitrogen atom;
• when x is 1, the linking arm D is attached to one of E, G, J, L or M;
• y may only take the value 1 when at least one of E, G, J, L and M is a divalent atom, and the radical R7 is carried by the nitrogen atom of the unsaturated ring;
• in the cationic groups of formula (IV):
• when x is 0, then the linking arm D is attached to the nitrogen atom carrying the radicals R8 to R10;
• when x is 1, then two of the radicals R8 to R10 conjointly form, with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring as, defined above and the linking arm D is carried by a carbon atom of the saturated ring;
• X− is chosen from monovalent and divalent anions;
• it being understood that:
• the number of unsaturated cationic groups Z of formula (II), in which at least one of E, G, J and L is a nitrogen atom is at least equal to 1;
• allowing said direct dyeing composition to remain in contact with said fibers for a time period ranging from approximately 3 to approximately 60 minutes;
• rinsing said fibers;
• and
• dying said fibers.