Symmetrical Cationic Tetraazo Compounds, for Dyeing Keratin Fibres

Compounds according to the preceding claim, characterized in that the radicals R1, independently of each other, represent a C1-C15 alkyl radical;

• a C2-C6 monohydroxyalkyl radical;
• a C2-C6 polyhydroxyalkyl radical;
• a (C1-C6)alkoxy(C2-C6)alkyl radical;
• an optionally substituted aryl radical, such as phenyl;
• an optionally substituted arylalkyl radical, such as benzyl;
• a C2-C6 amidoalkyl radical;
• a C2-C6 aminoalkyl radical in which the amine is substituted with two optionally substituted C1-C4 alkyl radicals, which may be identical or different;
• the radical R1 being linked to the nitrogen atom via a carbon atom.

Compounds according to any one of the preceding claims, characterized in that the radicals R2, R3 and R4, independently of each other, more particularly represent:

• a hydrogen atom;
• an optionally substituted C1-C16 and preferably C1-C8 alkyl radical;
• a halogen atom such as chlorine, fluorine or bromine;
• a hydroxyl group;
• a C1-C2 alkoxy radical;
• a C2-C4 (poly)hydroxyalkoxy radical;
• an amino radical, an amino radical substituted with one or two C1-C4 alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl or C1-C4 dialkylamino 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 hetero atom identical to or different from nitrogen;
• an alkylcarbonylamino radical (RCO—NR′—) in which the radical R represents a C1-C4 alkyl radical and the radical R′ represents a hydrogen atom or a C1-C4 alkyl radical;
• a carbamoyl radical ((R)2N—CO—) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group;
• an alkylsulfonylamino radical (R′SO2—NR—) in which the radical R represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the radical R′ represents a C1-C4 alkyl radical;
• an aminosulfonyl radical ((R)2N—SO2—) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group;
• a ureido radical (N(R)2—CO—NR′—) in which the radicals R and R′, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical.

Compounds according to any one of the preceding claims, characterized in that the radicals R2, R3 and R4, independently of each other, represent:

• a hydrogen atom;
• a C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, acylamino and amino radicals substituted with two identical or different C1-C2 alkyl radicals, optionally bearing at least one hydroxyl group, or a C1-C2 alkoxy radical;
• an amino radical;
• an amino radical substituted with one or two C1-C3 alkyl radicals, 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 hetero atom identical to or different from nitrogen;
• an acylamino radical;
• a carbamoyl radical;
• a sulfonylamino radical;
• a hydroxyl radical;
• a C1-C2 alkoxy radical;
• a chlorine atom.

Compounds according to any one of the preceding claims, characterized in that L represents the following formula:

• in which:
• D and D′, which are identical, represent a linear or branched C1-C14 hydrocarbon-based bond, which can form one or more 5- to 8-membered carbon-based rings, and which may be saturated or unsaturated, optionally interrupted with one or more hetero atoms or with one or more groups bearing at least one hetero atom, preferably chosen from oxygen and nitrogen;
• D and/or D′ are linked to the ammonium atom via a carbon atom;
• the bond a′ links the arms D and D′ to the groups W3, preferably via an oxygen atom or a nitrogen atom;
• y is greater than or equal to 1 and preferably equal to 1 or 2;
• the group R″ representing
• R5, R6, R15 and R′ 6, independently of each other, represent a C1-C15 alkyl radical;
• a C1-C6 monohydroxyalkyl radical;
• a C2-C6 polyhydroxyalkyl radical;
• a (C1-C6)alkoxy(C1-C6)alkyl radical;
• an aryl radical such as phenyl;
• an arylalkyl radical such as benzyl;
• a C1-C6 amidoalkyl radical;
• a C1-C6 aminoalkyl radical;
• a C1-C6 aminoalkyl radical in which the amine is substituted with one or more identical or different C1-C4 alkyl, (C1-C6)alkylcarbonyl, acylamino or (C1-C6)alkylsulfonyl radicals;
• R5 and R6 may form, together with the nitrogen atom to which they are attached, a 5-, 6- or 7-membered saturated cationic ring that may contain one or more hetero atoms, the cationic ring possibly being substituted with a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a C1-C6 alkoxy radical, an amido radical, a (C1-C6)alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6)alkylthio radical, an amino radical or an amino radical substituted with one or more identical or different C1-C6 alkyl, (C1-C6)alkylcarbonyl, acylamino or (C1-C6)alkylsulfonyl radicals;
• and preferably unsubstituted;
• R5 or R6 may form, with D or D′, a 5-, 6- or 7-membered saturated cationic ring that may contain one or more hetero atoms, the cationic ring possibly being substituted with a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxy-alkyl radical, a C2-C6 polyhydroxyalkyl radical, a C1-C6 alkoxy radical, an amido radical, a (C1-C6)alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6)alkylthio radical, an amino radical or an amino radical substituted with one or more identical or different C1-C6 alkyl, (C1-C6)alkylcarbonyl, acylamino or (C1-C6)alkylsulfonyl radicals;
• and preferably unsubstituted;
• the ring members E, G, J and M, which may be identical or different, represent a carbon, oxygen, sulfur or nitrogen atom to form a pyrazolium, imidazolium, triazolium, oxazolium, isoxazolium, thiazolium or isothiazolium ring,
• R7 represents a C1-C6 alkyl radical;
• a C1-C6 mono-hydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a (C1-C6)alkoxy(C1-C6)alkyl radical, a C2-C6 carbamylalkyl radical, a (C1-C6)alkylcarboxy(C1-C6)alkyl radical or a benzyl radical;
• it being understood that the radical R7 is borne by a nitrogen atom,
• R8, which may be identical or different, represent a hydrogen or halogen atom, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a hydroxyl radical, a C1-C6 alkoxy radical, an amido radical, a carboxyl radical, a C1-C6 alkylcarbonyl radical, a C1-C6 thioalkyl radical, a (C1-C6)alkylthio radical, an amino radical disubstituted with a (C1-C6)alkyl, (C1-C6)alkylcarbonyl or (C1-C6)alkylsulfonyl radical, a benzyl radical, a phenyl radical optionally substituted with one or more radicals chosen from methyl, hydroxyl, amino and methoxy radicals, it being understood that the radicals R8 are borne by a carbon atom,
• An represents one or more organic or mineral anions;
• z is an integer between 1 and 3;
• t is equal to 0 or 1;
• when t=0, then D′ is linked to the nitrogen atom via a carbon atom,
• v is an integer equal to 1 or 2,
• y is equal to 0 or 1.

Compounds according to any one of the preceding claims, characterized in that the cosmetically acceptable anion is chosen from halides such as chlorides, bromides, fluorides or iodides;

• hydroxides;
• sulfates;
• hydrogen sulfates;
• (C1-C6)alkyl sulfates;
• phosphates;
• carbonates;
• hydrogen carbonates, perchlorates;
• acetates;
• tartrates;
• citrates, oxalates;
• (C1-C6)alkylsulfonates such as methylsulfonate;
• arylsulfonates that are unsubstituted or substituted with a C1-C4 alkyl radical, for instance a 4-tolylsulfonate.

Dye composition comprising, in a medium that is suitable for dyeing keratin fibres, as direct dye, at least one symmetrical cationic tetraazo compound of formula (I) below:

• Dye1-L-Dye1
• in which formula:
• Dye1 represents:
• in which:
• W1, which are identical, represent a heteroaromatic radical chosen from the following formulae:
• W2, which are identical, represent a carbon-based aromatic group having the following formula:
• W3, which are identical, represent a carbon-based aromatic group having the following formula:
• L represents a C1-C60, preferably C2-C40 and even more particularly C2-C20 saturated or unsaturated, linear or branched, cyclic or non-cyclic, (hetero)aromatic or non-(hetero)aromatic, optionally substituted hydrocarbon-based chain, optionally bearing at least one cationic charge, optionally interrupted with at least one hetero atom or group comprising at least one hetero atom, preferably oxygen, nitrogen or sulfur, L not comprising any diazo, nitro, nitroso or peroxide groups;
• L may be terminated at one and the other of its ends with at least one hetero atom or group comprising at least one hetero atom, preferably oxygen, nitrogen or sulfur;
• R1, independently of each other, represent:
• a linear or branched, saturated or unsaturated, aromatic or non-aromatic, optionally substituted C1-C16 hydrocarbon-based chain, which can form one or more 3- to 7-membered carbon-based rings, optionally interrupted with one or more hetero atoms chosen from oxygen, nitrogen and sulfur;
• R1 not comprising any nitro, nitroso, peroxide or diazo bonds. R1 is directly attached to the nitrogen atom (quaternized or non-quaternized) of the heteroaromatic ring via a carbon atom;
• R2, R3 and R4, independently of each other, represent:
• a linear or branched, saturated or unsaturated, aromatic or non-aromatic, optionally substituted C1-C16 hydrocarbon-based chain, which can form one or more 3- to 6-membered carbon-based rings, optionally interrupted with one or more hetero atoms or with one or more groups bearing at least one hetero atom, preferably chosen from oxygen and nitrogen;
• a hydroxyl group,
• a C1-C4 alkoxy group,
• a C2-C4 (poly)hydroxyalkoxy group;
• an alkoxycarbonyl group (RO—CO—) in which R represents a C1-C4 alkyl radical, an alkylcarbonyloxy radical (RCO—O—) in which R represents a C1-C4 alkyl radical;
• an amino group, an amino group substituted with one or more C1-C4 alkyl radicals, 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 5- or 6-membered heterocycle optionally bearing another hetero atom identical to or different from nitrogen, for example oxygen or sulfur;
• an alkylcarbonylamino group (RCO—NR—) in which the radicals R, independently of each other, represent a C1-C4 alkyl radical;
• a carbamoyl group ((R)2N—CO) in which the radicals R, independently of each other, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;
• a ureido group ((R)2N—CO—NR′—) in which the radicals R and R′, independently of each other, represent a hydrogen atom or a C1-C4 alkyl radical;
• a sulfonamide group ((R)2N—SO2—) in which the radicals R, independently of each other, represent a hydrogen atom or a C1-C4 alkyl radical;
• an alkylsulfonylamino group (RSO2—NR′—) in which the radicals R and R′, independently of each other, represent a hydrogen atom or a C1-C4 alkyl radical;
• a guanidinium group ((R′)2N—C(═NH2+)—NR—) in which the radicals R and R′, independently of each other, represent a hydrogen atom or a C1-C4 alkyl radical;
• a nitro group;
• a cyano group;
• a halogen atom, preferably chlorine or fluorine;
• two radicals R2 or two radicals R3 or two radicals R4, borne by adjacent carbon atoms, can form, with the carbon atom to which each is attached, a fused ring:
• m represents an integer between 0 and 4;
• m′ represents an integer between 0 and 4;
• m″ represents an integer between 0 and 4;
• e is an integer between 0 and 2;
• the bond a derived from formula IIa, IIb, IIc, III or IV links the groups W1, W2 and W3 to the azo group;
• in the case of formulae IIa and IIc, and when two radicals R2 borne by two adjacent carbon atoms form an aromatic ring, the bond a may link the group W1 to the azo group via the said aromatic ring;
• the bond a′ derived from formula IV links the group W3 to the linker L;
• the electrical neutrality of the compounds being ensured by means of one or more cosmetically acceptable, identical or different anions An.