Anionic direct dye having a tetraalkylammonium counterion, dyeing composition comprising them and method for dyeing keratinous fibres starting from these dyes

A method for dyeing and lightening dark human keratinous fibers having a height of tone of less than or equal to 6, comprising:

• applying to the fibers, a composition comprising at least one fluorescent anionic dye of formula (I)
• and optical isomers, geometric isomers, and solvates thereof, wherein in formula (I):
• R1, R2, R3 and R4, which are identical, are chosen from i) linear (C1-C6)alkyls;
• and ii) linear (C2-C6)alkenyls;
• it being possible for the alkyl or alkenyl group of the groups of i) and ii) to be interrupted by at least one identical or different heteroatoms chosen from oxygen, sulphur, and N(Rα), wherein Rα is chosen from hydrogen atoms and alkyl groups;
• Col(−)m represents the anionic part of the anionic dye comprising at least one sulphonate group and/or at least one carboxylate group, and wherein m is the anionic charges;
• wherein m and n, which are identical or different, represent an integer ranging from 1 to 10;
• wherein when the anionic part of the anionic dye comprises a sulphonate group or a carboxylate group, then m=n=1;
• wherein when the anionic part of the anionic dye comprises anionic groups other than a sulphonate or carboxylate group, the anionic part is combined with at least one cationic counterion, organic, inorganic or R1R2R3R4N+, making it possible to achieve electrical neutrality of the formula (I);
• and
• the at least one anionic dye of formula (I) is chosen from the dyes of formulae (II), (II′), (III), or (III′):
• a) diaryl anionic azo dyes of formula (II) or (II′):
• wherein in formulae (II) and (II′):
• R7, R8, R9, R10, R′7, R′8, R′9 and R′10, which are identical or different, are chosen from a hydrogen atom or a group chosen from:
• alkyl groups;
• alkoxy groups or alkylthio groups;
• hydroxyl groups or mercapto groups;
• nitro groups or nitroso groups;
• R∘—C(X)—X′—, R∘—X′—C(X)—, R∘—X′—C(X)—X″—, wherein R∘ is chosen from a hydrogen atom, alkyl groups, or aryl groups;
• and X, X′ and X″, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group;
• M+(O)2S(O−)—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• M+(O)CO−—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R″—S(O)2—, wherein R″ is chosen from hydrogen atoms, or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group;
• R″′—S(O)2—X′—, wherein R″′ is chosen from an alkyl group or an aryl group which is optionally substituted, and X′ is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group;
• (di)(alkyl)amino groups;
• aryl(alkyl)amino, optionally substituted by at least one group chosen from i) nitro;
• ii) nitroso;
• iii) M+(O)2S(O−)— or iv) alkoxy groups, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• optionally substituted heteroaryl groups;
• cycloalkyl groups;
• Ar—N═N—, wherein Ar is an optionally substituted aryl group;
• or else two contiguous groups, R7 with R8, R8 with R9, or R9 with R10, together form a fused benzo group A′;
• and R′7 with R′8 or R′8 with R′9 or R′9 with R′10 together form a fused benzo group B′;
• with A′ and B′ optionally substituted by one or more groups chosen from i) nitro;
• ii) nitroso;
• iii) M+(O)2S(O−)—;
• iv) hydroxyl;
• v) mercapto;
• vi) (di)(alkyl)amino;
• vii) R∘—C(X)—X′—;
• viii) R∘—X′—C(X)—;
• ix) R∘—X′—C(X)—X″—;
• x) Ar—N═N— and xi) aryl(alkyl)amino which is optionally substituted, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• W is chosen from a sigma σ bond, an oxygen or sulphur atom or a divalent radical i) —NR—, or ii) methylene —C(Ra)(Rb)—, wherein Ra and Rb, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else Ra and Rb form, together with the carbon atom which carries them, a spirocycloalkyl;
• with the proviso that the formulae (II) and (II′) comprise at least one sulphonate radical R1R2R3R4N+(O)2S(O−)— or carboxylate radical R1R2R3R4N+(O)C(O−)— on one of the rings A, A′, B, B′ or C;
• or
• b) pyrazolone anionic azo dyes of formulae (III) or (III′):
• wherein in formulae (III) and (III′):
• R11, R12 and R13, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group or an M+(O)2S(O−)— group, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R14 is chosen from a hydrogen atom, an alkyl group or an M+C(O)O− group, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R15 represents a hydrogen atom;
• R16 represents an oxo group, in which case R′16 is absent, or else R15 with R16 together form a double bond;
• R17 and R18, which are identical or different, are chosen from a hydrogen atom or a group chosen from:
• M+(O)2S(O−)—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• Ar—O—S(O)2—, wherein Ar is an optionally substituted aryl group;
• R19 and R20, together form either a double bond or an optionally substituted benzo group D′;
• R′16, R′19 and R′20, which are identical or different, are chosen from a hydrogen atom, an alkyl group, or a hydroxyl group;
• R21 is chosen from a hydrogen atom, an alkyl group, or an alkoxy group;
• Ra and Rb, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else Ra and Rb form, together with the carbon atom which carries them, a spirocycloalkyl;
• Y is chosen from a hydroxyl group or an oxo group;
• represents a single bond when Y is an oxo group and represents a double bond when Y represents a hydroxyl group;
• with the proviso that the formulae (III) and (III′) comprise at least one sulphonate group R1R2R3R4N+(O)2S(O−)— on one of the rings D or E or the formulae (III) and (III′) comprise at least one carboxylate group R1R2R3R4N+(O)C(O−)—.

An anionic dye for dyeing human keratinous fibers of formula (I):

• and optical isomers, geometric isomers, and solvates thereof, wherein in formula (I):
• R1, R2, R3 and R4, which are identical, are chosen from i) linear (C1-C6)alkyls;
• and ii) linear (C2-C6)alkenyls;
• it being possible for the alkyl or alkenyl group of the groups of i) and ii) to be interrupted by at least one identical or different heteroatoms chosen from oxygen, sulphur, and N(Rα), wherein Rα is chosen from hydrogen atoms and alkyl groups;
• Col(−)m represents the anionic part of the anionic dye comprising at least one sulphonate group and/or at least one carboxylate group and wherein m is the anionic charges;
• wherein m and n, which are identical or different, represent an integer ranging from 1 to 10;
• wherein:
• when the anionic part of the anionic dye comprises a sulphonate group or a carboxylate group, then m=n=1;
• when the anionic part of the anionic dye comprises anionic groups other than a sulphonate or carboxylate group, the anionic part is combined with at least one cationic counterion, organic, inorganic or R1R2R3R4N+, making it possible to achieve electrical neutrality of the formula (I),
• the at least one anionic dye of formula (I) is chosen from the dyes of formulae (II), (II′), (III), or (III′):
• a) diaryl anionic azo dyes of formula (II) or (II′):
• wherein in formulae (II) and (II′):
• R7, R8, R9, R10, R′7, R′8, R′9 and R′10, which are identical or different, are chosen from a hydrogen atom or a group chosen from:
• alkyl groups;
• alkoxy groups or alkylthio groups;
• hydroxyl groups or mercapto groups;
• nitro groups or nitroso groups;
• R∘—C(X)—X′—, R∘—X′—C(X)—, R∘—X′—C(X)—X″—, wherein R∘ is chosen from a hydrogen atom, alkyl groups, or aryl groups;
• and X, X′ and X″, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group;
• M+(O)2S(O−)—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• M+(O)CO−—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R″—S(O)2—, wherein R″ is chosen from hydrogen atoms, or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group;
• R″′—S(O)2—X′—, wherein R″′ is chosen from an alkyl group or an aryl group which is optionally substituted, and X′ is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group;
• (di)(alkyl)amino groups;
• aryl(alkyl)amino, optionally substituted by at least one group chosen from i) nitro;
• ii) nitroso;
• iii) M+(O)2S(O−)— or iv) alkoxy groups, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• optionally substituted heteroaryl groups;
• cycloalkyl groups;
• Ar—N═N—, wherein Ar is an optionally substituted aryl group;
• or else two contiguous groups, R7 with R8, R8 with R9, or R9 with R10, together form a fused benzo group A′;
• and R′7 with R′8 or R′8 with R′9 or R′9 with R′10 together form a fused benzo group B′;
• with A′ and B′ optionally substituted by one or more groups chosen from i) nitro;
• ii) nitroso;
• iii) M+(O)2S(O−)—;
• iv) hydroxyl;
• v) mercapto;
• vi) (di)(alkyl)amino;
• vii) R∘—C(X)—X′—;
• viii) R∘—X′—C(X)—;
• ix) R∘—X′—C(X)—X″—;
• x) Ar—N═N— and xi) aryl(alkyl)amino which is optionally substituted, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• W is chosen from a sigma a bond, an oxygen or sulphur atom or a divalent radical i) —NR—, or ii) methylene —C(Ra)(Rb)—, wherein Ra and Rb, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else Ra and Rb form, together with the carbon atom which carries them, a spirocycloalkyl;
• with the proviso that the formulae (II) and (II′) comprise at least one sulphonate radical R1R2R3R4N+(O)2S(O−)— or carboxylate radical R1R2R3R4N+(O)C(O−)— on one of the rings A, A′, B, B′ or C;
• or
• b) pyrazolone anionic azo dyes of formulae (III) or (III′):
• wherein in formulae (III) and (III′):
• R11, R12 and R13, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group or an M+(O)2S(O−)— group, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R14 is chosen from a hydrogen atom, an alkyl group or an M+C(O)O− group, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R15 represents a hydrogen atom;
• R16 represents an oxo group, in which case R′16 is absent, or else R15 with R16 together form a double bond;
• R17 and R18, which are identical or different, are chosen from a hydrogen atom or a group chosen from:
• M+(O)2S(O−)—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• Ar—O—S(O)2—, wherein Ar is an optionally substituted aryl group;
• R19 and R20, together form either a double bond or an optionally substituted benzo group D′;
• R′16, R′19 and R′20, which are identical or different, are chosen from a hydrogen atom, an alkyl group, or a hydroxyl group;
• R21 is chosen from a hydrogen atom, an alkyl group, or an alkoxy group;
• Ra and Rb, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else Ra and Rb form, together with the carbon atom which carries them, a spirocycloalkyl;
• Y is chosen from a hydroxyl group or an oxo group;
• represents a single bond when Y is an oxo group and represents a double bond when Y represents a hydroxyl group;
• with the proviso that the formulae (III) and (III′) comprise at least one sulphonate group R1R2R3R4N+(O)2S(O−)— on one of the rings D or E or the formulae (III) and (III′) comprise at least one carboxylate group R1R2R3R4N+(O)C(O−)—;
• wherein the anionic dye of formula (I) is different from the dyes of formulae (a) to (u):

A dyeing composition for dyeing human keratinous fibers, said composition comprising at least one anionic dye of formula (I):

• and optical isomers, geometric isomers, and solvates thereof, wherein in formula (I):
• R1, R2, R3 and R4, which are identical, are chosen from i) linear (C1-C6)alkyls;
• and ii) linear (C2-C6)alkenyls;
• it being possible for the alkyl or alkenyl group of the groups of i) and ii) to be interrupted by at least one identical or different heteroatoms chosen from oxygen, sulphur, and N(Rα), wherein Rα is chosen from hydrogen atoms and alkyl groups;
• Col(−)m represents the anionic part of the anionic dye comprising at least one sulphonate group and/or at least one carboxylate group and wherein m is the anionic charges;
• wherein m and n, which are identical or different, represent an integer ranging from 1 to 10;
• wherein:
• when the anionic part of the anionic dye comprises a sulphonate group or a carboxylate group, then m=n=1;
• when the anionic part of the anionic dye comprises anionic groups other than a sulphonate or carboxylate group, the anionic part is combined with at least one cationic counterion, organic, inorganic or R1R2R3R4N+, making it possible to achieve electrical neutrality of the formula (I),
• the at least one anionic dye of formula (I) is chosen from the dyes of formulae (II), (II′), (III), or (III′):
• a) diaryl anionic azo dyes of formula (II) or (II′):
• wherein in formulae (II) and (II′):
• R7, R8, R9, R10, R′7, R′8, R′9 and R′10, which are identical or different, are chosen from a hydrogen atom or a group chosen from:
• alkyl groups;
• alkoxy groups or alkylthio groups;
• hydroxyl groups or mercapto groups;
• nitro groups or nitroso groups;
• R∘—C(X)—X′—, R∘—X′—C(X)—, R∘—X′—C(X)—X″—, wherein R∘ is chosen from a hydrogen atom, alkyl groups, or aryl groups;
• and X, X′ and X″, which are identical or different, are chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group;
• M+(O)2S(O−)—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• M+(O)CO−—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R″—S(O)2—, wherein R″ is chosen from hydrogen atoms, or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group;
• R″′—S(O)2—X′—, wherein R″′ is chosen from an alkyl group or an aryl group which is optionally substituted, and X′ is chosen from oxygen atoms, sulphur atoms, or NR, wherein R is chosen from a hydrogen atom or an alkyl group;
• (di)(alkyl)amino groups;
• aryl(alkyl)amino, optionally substituted by at least one group chosen from i) nitro;
• ii) nitroso;
• iii) M+(O)2S(O−)— or iv) alkoxy groups, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• optionally substituted heteroaryl groups;
• cycloalkyl groups;
• Ar—N═N—, wherein Ar is an optionally substituted aryl group;
• or else two contiguous groups, R7 with R8, R8 with R9, or R9 with R10, together form a fused benzo group A′;
• and R′7 with R′8 or R′8 with R′9 or R′9 with R′10 together form a fused benzo group B′;
• with A′ and B′ optionally substituted by one or more groups chosen from i) nitro;
• ii) nitroso;
• iii) M+(O)2S(O−)—;
• iv) hydroxyl;
• v) mercapto;
• vi) (di)(alkyl)amino;
• vii) R∘—C(X)—X′—;
• viii) R∘—X′—C(X)—;
• ix) R∘—X′—C(X)—X″—;
• x) Ar—N═N— and xi) aryl(alkyl)amino which is optionally substituted, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• W is chosen from a sigma σ bond, an oxygen or sulphur atom or a divalent radical i) —NR—, or ii) methylene —C(Ra)(Rb)—, wherein Ra and Rb, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else Ra and Rb form, together with the carbon atom which carries them, a spirocycloalkyl;
• with the proviso that the formulae (II) and (II′) comprise at least one sulphonate radical R1R2R3R4N+(O)2S(O−)— or carboxylate radical R1R2R3R4N+(O)C(O−)— on one of the rings A, A′, B, B′ or C;
• or
• b) pyrazolone anionic azo dyes of formulae (III) or (III′):
• wherein in formulae (III) and (III′):
• R11, R12 and R13, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group or an M+(O)2S(O−)— group, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R14 is chosen from a hydrogen atom, an alkyl group or an M+C(O)O− group, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• R15 represents a hydrogen atom;
• R16 represents an oxo group, in which case R′16 is absent, or else R15 with R16 together form a double bond;
• R17 and R18, which are identical or different, are chosen from a hydrogen atom or a group chosen from:
• M+(O)2S(O−)—, wherein M+ is chosen from hydrogen atoms, cationic counterions, or cationic counterions R1R2R3R4N+;
• Ar—O—S(O)2—, wherein Ar is an optionally substituted aryl group;
• R19 and R20, together form either a double bond or an optionally substituted benzo group D′;
• R′16, R′19 and R′20, which are identical or different, are chosen from a hydrogen atom, an alkyl group, or a hydroxyl group;
• R21 is chosen from a hydrogen atom, an alkyl group, or an alkoxy group;
• Ra and Rb, which are identical or different, are chosen from a hydrogen atom or an aryl group, or else Ra and Rb form, together with the carbon atom which carries them, a spirocycloalkyl;
• Y is chosen from a hydroxyl group or an oxo group;
• represents a single bond when Y is an oxo group and represents a double bond when Y represents a hydroxyl group;
• with the proviso that the formulae (III) and (III′) comprise at least one sulphonate group R1R2R3R4N+(O)2S(O−)— on one of the rings D or E or the formulae (III) and (III′) comprise at least one carboxylate group R1R2R3R4N+(O)C(O−)—;
• the anionic dye of formula (I) is different from the dyes of formulae (a) to (u):