FLUORESCENT DIRECT DYE BEARING AN ALIPHATIC CHAIN AND A DISULFIDE/THIOL/PROTECTED-THIOL FUNCTION FOR DYEING KERATIN MATERIALS

Abstract

The invention relates to a process for dyeing and/or lightening keratin materials, in particular keratin fibres, preferably human keratin fibres such as the hair, using at least one fluorescent direct dye bearing a disulfide, thiol or protected-thiol function and comprising at least one aliphatic chain of formula (I). The invention also relates to the use i) of at least one fluorescent direct dye bearing a disulfide, thiol or protected-thiol function (I) combined with ii) steam and/or a heating iron for straightening keratin fibres, for dyeing and lightening keratin materials, and to novel fluorescent direct dyes bearing a disulfide, thiol or protected-thiol function of formula (I), and also a cosmetic composition comprising same.

The process used and the use of the thiol, protected-thiol or disulfide fluorescent direct dyes of formula (I) combined with steam makes it possible especially to obtain long-lasting colouring with care valency on keratin materials.

Claims

1.-20. (canceled)

21. A process for dyeing keratin materials, comprising applying to the keratin materials at least one cationic, anionic, neutral, or zwitterionic fluorescent direct dye bearing a disulfide function or a thiol or protected-thiol function chosen from compounds of formula (I):
A-(X).sub.pC.sub.satSU(I), salts thereof with organic or mineral acids or bases, optical or geometric isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (I): U represents a radical chosen from: a) SC.sub.sat(X).sub.p-A; and b) Y; A and A, which may be identical or different, represent a cationic, anionic, nonionic or zwitterionic fluorescent chromophore, it being understood that at least one of the two chromophores bears at least one linear or branched, saturated or unsaturated C.sub.10-C.sub.30 aliphatic chain; Y represents i) a hydrogen atom; or ii) a thiol-function protecting group; X and X, which may be identical or different, represent a linear or branched, saturated or unsaturated divalent C.sub.1-C.sub.30 hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from: N(R), N.sup.+(R)(R.sup.o), O, C(O), S(O) and S(O).sub.2, with R and R.sup.o, which may be identical or different, chosen from a hydrogen, a C.sub.1-C.sub.4 alkyl, hydroxyalkyl, or aminoalkyl radical; an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms; p and p, which may be identical or different, are equal to 0 or 1; C.sub.sat and C.sub.sat, which may be identical or different, represent an optionally cyclic, optionally substituted, linear or branched C.sub.1-C.sub.18 alkylene chain; wherein the electrical neutrality of the compounds of formula (I) may be ensured by one or more anionic or, respectively, cationic counterions depending on whether the dye is cationic or, respectively, anionic.

22. The process according to claim 21, wherein the dye(s) of formula (I) are disulfide dyes with U representing a radical a) SC.sub.sat(X).sub.p-A; wherein formula (I) has the following formula:
A-(X).sub.pC.sub.satSSC.sub.sat(X).sub.p-A with A=A,X=X,p=p,C.sub.sat=C.sub.sat.

23. The process according to claim 21, wherein the at least one dye of formula (I) is a dye bearing a thiol or protected-thiol function, wherein U represents the radical b) Y, wherein Y represents a hydrogen atom.

24. The process according to claim 21, wherein the at least one dye of formula (I) is a dye with C.sub.sat and C.sub.sat, which may be identical or different, representing a chain (CH.sub.2).sub.k with k being an integer between 1 and 8 inclusive.

25. The process according to claim 21, wherein the at least one dye of formula (I) is a dye which, when p and p is equal to 1, X and X, which may be identical or different, represent the following sequence:
-(T).sub.t-(Z).sub.z-(T).sub.t- said sequence being linked in formula (I) symmetrically as follows:
C.sub.sat-(T).sub.t-(Z).sub.z-(T).sub.t-A or C.sub.sat-(T).sub.t-(Z).sub.z-(T).sub.t-A; wherein: T and T, which may be identical or different, represent one or more radicals or combinations thereof chosen from: O; S; N(R); N.sup.+(R)(R.sup.o); S(O); S(O).sub.2; C(O); with R, R.sup.o, which may be identical or different, representing a hydrogen atom, a C.sub.1-C.sub.4 alkyl radical, C.sub.1-C.sub.4 hydroxyalkyl radical, or an aryl(C.sub.1-C.sub.4)alkyl radical; and a cationic or non-cationic heterocycloalkyl or heteroaryl radical; t and t, which may be identical or different, are equal to 0 or 1; Z represents: (CH.sub.2).sub.m with m being an integer between 1 and 8; (CH.sub.2CH.sub.2O).sub.q or (OCH.sub.2CH.sub.2).sub.q wherein q is an integer between 1 and 5 inclusive; an aryl, alkylaryl, or arylalkyl radical in which the alkyl radical is C.sub.1-C.sub.4, being optionally substituted with at least one group SO.sub.3M with M representing a hydrogen atom, an alkali metal, or an ammonium group substituted with one or more identical or different, linear or branched C.sub.1-C.sub.8 alkyl radicals optionally bearing at least one hydroxyl; z is 0 or 1.

26. The process according to claim 21, wherein the at least one dye of formula (I) comprises a cationic, anionic, neutral, or zwitterionic fluorescent chromophore, A and/or A, which may be identical or different, derived from dyes of the following types: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanines; (poly)methines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids; fluorindines; formazans; indamines; indanthrones; indigoids; pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes; or xanthenes.

27. The process according to claim 21, wherein the keratin materials have a tone depth of less than or equal to 6 before the application.

28. The process according to claim 21, wherein the at least one dye of formula (I) comprises a cationic fluorescent chromophore A and/or A which contains at least one quaternary ammonium radical bearing an aliphatic chain chosen from: a) the polymethine radicals of formulae (II) and (II) below: ##STR00050## wherein formula (II) or (II): W.sup.+ represents a cationic heterocyclic or heteroaryl group, comprising a quaternary ammonium bearing an aliphatic chain, said heterocyclic or heteroaryl group being optionally substituted with one or more (C.sub.1-C.sub.8)alkyl groups optionally substituted with one or more hydroxyl groups; W.sup.+ represents a cationic heterocyclic or heteroaryl divalent radical comprising a quaternary ammonium, said heterocyclic or heteroaryl group being optionally substituted with one or more (C.sub.1-C.sub.8)alkyl groups optionally substituted with one or more hydroxyl groups; Ar represents an aryl group bearing an exocyclic ammonium charge, with an aliphatic chain, optionally substituted with i) one or more halogen atoms; ii) one or more (C.sub.1-C.sub.8)alkyl groups; iii) one or more hydroxyl groups; iv) one or more (C.sub.1-C.sub.8)alkoxy groups; v) one or more hydroxy(C.sub.1-C.sub.8)alkyl groups, vi) one or more amino or (di)(C.sub.1-C.sub.8)alkylamino groups; vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups; Ar is a divalent aryl radical chosen from phenyl or naphthyl, optionally substituted with i) one or more halogen atoms; ii) one or more (C.sub.1-C.sub.8)alkyl; iii) one or more hydroxyl groups; iv) one or more (C.sub.1-C.sub.8)alkoxy groups; v) one or more hydroxy(C.sub.1-C.sub.8)alkyl groups, vi) one or more amino or (di)(C.sub.1-C.sub.8)alkylamino groups, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups chosen from piperazinyl, piperidyl, or 5- or 6-membered heteroaryl; m represents an integer between 1 and 4 inclusive; R.sup.c and R.sup.d, which may be identical or different, represent a hydrogen atom or an optionally substituted (C.sub.1-C.sub.8)alkyl group, or alternatively R.sup.c contiguous with W.sup.+ or W.sup.+ and/or R.sup.d contiguous with Ar or Ar form, with the atoms that bear them, a (hetero)cycloalkyl; Q.sup., which may be present or absent, is an anionic counterion which serves to ensure the electrical neutrality of the molecule; (*) represents the part of the chromophore linked to the rest of formula (I); wherein at least one of the groups W.sup.+, W.sup.+, Ar, or Ar bears at least one ammonium group bearing a linear or branched, saturated or unsaturated C.sub.10-C.sub.30 aliphatic chain; b) the naphthalimidyl radicals of formula (III) or (III) below: ##STR00051## in which formulae (III) and (III) R.sup.e, R.sup.f, R.sup.g and R.sup.h, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.6 alkyl group, of which at least one of the groups R.sup.e or R.sup.f of the naphthalimidyl (III), or alternatively R.sup.g or R.sup.h of the naphthalimidyl (IV) is substituted with a trialkylammonium group R.sub.aR.sub.bR.sub.cN.sup.+, An.sup., with R.sub.a and R.sub.b, which may be identical or different, representing a (C.sub.1-C.sub.30)alkyl group and R.sub.c representing a C.sub.10-C.sub.30, and An.sup., which may be present or absent, representing an anionic counterion which ensures the electrical neutrality of the molecule.

29. The process according to claim 21, wherein the at least one dye of formula (I) is a disulfide dye chosen from those of formulae (IV) to (VIII) and thiol or protected-thiol dyes chosen from those of formulae (IV) to (VIII) below: ##STR00052## ##STR00053## organic or mineral acid salts, optical isomers and geometrical isomers thereof, or solvates thereof; in which formulae (IV) to (VIII) and (IV) to (VIII): G and G, which may be identical or different, represent i) a group NR.sub.cR.sub.d, NR.sub.cR.sub.d, ii) C.sub.1-C.sub.6 alkoxy which is optionally substituted; or iii) a group R.sup.1R.sup.2R.sup.3N.sup.+, An.sup. with R.sup.1 representing a linear or branched (C.sub.10-C.sub.30)alkyl; and R.sup.2 and R.sup.3, which may be identical or different, represent a linear or branched (C.sub.1-C.sub.30) alkyl group, and An.sup., which may be present or absent, represents an organic or mineral anionic counterion; R.sub.a and R.sub.a, which may be identical or different, represent an aryl(C.sub.1-C.sub.4)alkyl group or a C.sub.1-C.sub.6 alkyl group optionally substituted with a hydroxyl or amino, C.sub.1-C.sub.4 alkylamino or C.sub.1-C.sub.4 dialkylamino group, said alkyl radicals optionally forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or non-nitrogen heteroatom; R.sub.b and R.sub.b, which may be identical or different, represent a hydrogen atom, an aryl(C.sub.1-C.sub.4)alkyl group, or a C.sub.1-C.sub.6 alkyl group that is optionally substituted; R.sub.c, R.sub.c, R.sub.d and R.sub.d, which may be identical or different, represent a hydrogen atom, an aryl(C.sub.1-C.sub.4)alkyl, C.sub.1-C.sub.6 alkoxy group, or a C.sub.1-C.sub.6 alkyl group that is optionally substituted; or alternatively two adjacent radicals R.sub.c and R.sub.d, R.sub.c and R.sub.d borne by the same nitrogen atom together form a heterocyclic or heteroaryl group; R.sub.e and R.sub.e, which may be identical or different, represent a linear or branched, optionally unsaturated, divalent C.sub.1-C.sub.6 alkylenyl hydrocarbon-based chain; R.sub.f and R.sub.f, which may be identical or different, represent a quaternary ammonium group R.sup.1R.sup.2R.sup.3N.sup.+; R.sub.g, R.sub.g, R.sub.g, R.sub.g, R.sub.h, R.sub.h, R.sub.h and R.sub.h, which may be identical or different, represent a hydrogen atom, a halogen atom, an amino, C.sub.1-C.sub.4 alkylamino, C.sub.1-C.sub.4 dialkylamino, cyano, carboxyl, hydroxyl group, trifluoromethyl group, an acylamino, C.sub.1-C.sub.4 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, alkylcarbonyloxy, alkoxycarbonyl radical, alkylcarbonylamino radical, an acylamino, carbamoyl or alkylsulfonylamino radical, an aminosulfonyl radical, or a C.sub.1-C.sub.16 alkyl radical optionally substituted with a group chosen from C.sub.1-C.sub.12 alkoxy, hydroxyl, cyano, carboxyl, amino, C.sub.1-C.sub.4 alkylamino, or C.sub.1-C.sub.4 dialkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another heteroatom identical to or different from that of the nitrogen atom; or alternatively two groups R.sub.g and R.sub.g; R.sub.g and R.sub.g; R.sub.h and R.sub.h; R.sub.h and R.sub.h borne by two adjacent carbon atoms together form a benzo or indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted with a halogen atom, an amino, C.sub.1-C.sub.4 alkylamino, C.sub.1-C.sub.4 dialkylamino, nitro, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, C.sub.1-C.sub.4 alkoxy, (poly)hydroxy(C.sub.2-C.sub.4)alkoxy, alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical, an acylamino, carbamoyl or alkylsulfonylamino radical, an aminosulfonyl radical, or a C.sub.1-C.sub.16 alkyl radical optionally substituted with: a group chosen from C.sub.1-C.sub.12 alkoxy, hydroxyl, cyano, carboxyl, amino, C.sub.1-C.sub.4 alkylamino, C.sub.1-C.sub.4 dialkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another heteroatom identical to or different from that of the nitrogen atom; or alternatively when G represents NR.sub.cR.sub.d and G represents NR.sub.cR.sub.d, two groups R.sub.c and R.sub.g; R.sub.c and R.sub.g; R.sub.d and R.sub.g; R.sub.d and R.sub.g together form a saturated heteroaryl or heterocycle, optionally substituted with one or more groups C.sub.1-C.sub.6 alkyl; R.sub.i, R.sub.i, R.sub.i and R.sub.i, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl group; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may be identical or different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.12 alkoxy, hydroxyl, cyano, carboxyl, amino, C.sub.1-C.sub.4 alkylamino or C.sub.1-C.sub.4 dialkylamino group, said alkyl radicals possibly forming with the nitrogen atom that bears them a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; T.sub.a and T.sub.b, which may be identical or different, represent i) a covalent bond, ii) or one or more radicals or combinations thereof chosen from SO.sub.2, O, S, N(R), N.sup.+(R)(R.sup.o) and CO, with R and R.sup.o, which may be identical or different, representing a hydrogen atom, a C.sub.1-C.sub.4 alkyl radical or a C.sub.1-C.sub.4 hydroxyalkyl radical, or an aryl(C.sub.1-C.sub.4)alkyl radical; ##STR00054## which may be identical or different, represent a heterocyclic group, which is optionally substituted with a quaternary ammonium group R.sup.1R.sup.2R.sup.3N.sup.+; ##STR00055## represents an aryl or heteroaryl group fused to the imidazolium or phenyl ring; or alternatively is absent from the imidazolium or phenyl ring; m, m, n and n, which may be identical or different, represent an integer between 0 and 6 inclusive, with m+n and m+n, which may be identical or different, representing an integer between 1 and 10 inclusive; Y represents a hydrogen atom or a protecting group chosen from: (C.sub.1-C.sub.4)alkylcarbonyl, for instance methylcarbonyl or ethylcarbonyl; arylcarbonyl, for instance phenylcarbonyl; (C.sub.1-C.sub.4)alkoxycarbonyl; aryloxycarbonyl; aryl(C.sub.1-C.sub.4)alkoxycarbonyl; (di)(C.sub.1-C.sub.4)(alkyl)aminocarbonyl; (C.sub.1-C.sub.4)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; cationic 5- or 6-membered monocyclic heteroaryl; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups; cationic 8- to 11-membered bicyclic heteroaryl; these groups being optionally substituted with one or more identical or different (C.sub.1-C.sub.4)alkyl groups; cationic heterocycle having the following formula: ##STR00056## C(NH.sub.2)N.sup.+H.sub.2; An.sup.; C(NH.sub.2)NH; SO.sub.3.sup., M.sup.+ with M.sup.+ representing an alkali metal; and M represents an anionic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the dye molecule; wherein at least one of the groups G, G, R.sub.a, R.sub.a, R.sub.c, R.sub.c, R.sub.d, R.sub.d, R.sub.f or R.sub.f bears at least one group R.sup.1R.sup.2R.sup.3N.sup.+.

30. The process according to claim 21, wherein the at least one dye of formula (I) is chosen from those of formulae (IX) to (X): ##STR00057## organic or mineral acid salts, optical isomers or geometrical isomers thereof, or the solvates; wherein formulae (IX) to (X): G and G, which may be identical or different, represent i) a (di)(C.sub.1-C.sub.6)alkylamine group with at least one of the alkyl groups substituted with an ammonium group R.sup.1R.sup.2R.sup.3N.sup.+ or ii) an ammonium group R.sup.1R.sup.2R.sup.3N.sup.+; R.sub.g, R.sub.g, R.sub.g, R.sub.g, R.sub.h, R.sub.h, R.sub.h and R.sub.h, which may be identical or different, represent a hydrogen or halogen atom, an amino, (di)(C.sub.1-C.sub.4)alkylamino, cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C.sub.1-C.sub.4 alkoxy, C.sub.2-C.sub.4 (poly)hydroxyalkoxy, (C.sub.1-C.sub.4)alkylcarbonyloxy, (C.sub.1-C.sub.4)alkoxycarbonyl, (C.sub.1-C.sub.4)alkylcarbonylamino, acylamino, carbamoyl or (C.sub.1-C.sub.4)alkylsulfonylamino group, an aminosulfonyl radical or a (C.sub.1-C.sub.16)alkyl radical optionally substituted with a group chosen from (C.sub.1-C.sub.12)alkoxy, hydroxyl, cyano, carboxyl, amino and (di)(C.sub.1-C.sub.4)alkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom; R.sub.i, R.sub.i, R.sub.i and R.sub.i, which may be identical or different, represent a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; in particular R.sub.i, R.sub.i, R.sub.i, and R.sub.i represent a hydrogen atom; T.sub.a and T.sub.b, which may be identical or different, represent i) either a covalent bond, ii) or one or more radicals or combinations thereof chosen from O, N(R) and C(O), with R representing a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical m, m, n and n, which may be identical or different, represent an integer between 0 and 6 inclusive, with m+n and m+n, which may be identical or different, representing an integer between 1 and 10 inclusive; wherein the bond between the pyridinium ring and the double bond of the ethylene or styryl group is located in position 2 or 4 of the pyridinium.

31. The process according to claim 21, wherein the at least one dye of formula (I) is chosen from those below: ##STR00058## ##STR00059## ##STR00060## ##STR00061## and also organic or mineral acid salts and geometrical isomers thereof, and solvates thereof; with An.sup., M, which may be identical or different, representing anionic counterions.

32. The process according to claim 21, wherein the at least one dye of formula (I) is chosen from (A) and (B) below: ##STR00062## and also organic or mineral acid salts thereof, geometrical isomers thereof, or solvates thereof; in which formulae (A) and (B): R, which are identical, represent a linear (C.sub.10-C.sub.30)alkyl group; R, which are identical, represent a linear (C.sub.10-C.sub.30)alkyl group; and An.sup., which may be identical or different, is chosen from a halide.

33. The process according to claim 21, wherein the process comprises i) applying to the keratin materials at least one fluorescent dye bearing a disulfide, thiol or protected-thiol function of formula (I) and ii) applying to the keratin materials a heat source chosen from steam or a straightening iron.

34. The process according to claim 33, wherein applying steam to the keratin materials is performed after applying to the keratin materials i) at least one fluorescent direct dye bearing a disulfide function, a thiol, or protected-thiol function.

35. The process according to claim 21, wherein the process does not use a reducing agent.

36. The process according to claim 21, wherein the process does not use a chemical oxidizing agent.

37. The process according to claim 21, wherein the tone depth of the keratin materials is less than or equal to 4.

38. A compound chosen from compounds of formula (I):
A-(X).sub.pC.sub.satSU(I), salts thereof with organic or mineral acids or bases, optical or geometric isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (I): U represents a radical chosen from: a) SC.sub.sat(X).sub.p-A; and b) Y; A and A, which may be identical or different, represent a cationic, anionic, nonionic or zwitterionic fluorescent chromophore, it being understood that at least one of the two chromophores bears at least one linear or branched, saturated or unsaturated C.sub.10-C.sub.30 aliphatic chain; Y represents i) a hydrogen atom; or ii) a thiol-function protecting group; X and X, which may be identical or different, represent a linear or branched, saturated or unsaturated divalent C.sub.1-C.sub.30 hydrocarbon-based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from: N(R), N.sup.+(R)(R.sup.o), O, C(O), S(O) and S(O).sub.2, with R and R.sup.o, which may be identical or different, chosen from a hydrogen, a C.sub.1-C.sub.4 alkyl, hydroxyalkyl, or aminoalkyl radical; an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms; p and p, which may be identical or different, are equal to 0 or 1; C.sub.sat and C.sub.sat, which may be identical or different, represent an optionally cyclic, optionally substituted, linear or branched C.sub.1-C.sub.18 alkylene chain; wherein the electrical neutrality of the compounds of formula (I) may be ensured by one or more counterions.

39. A composition comprising at least one compound of claim 38.

Description

EXAMPLES

Example A: Disulfide Dyes Bearing a Naphthalimide Chromophore of Formula (A) Below

[0413] ##STR00033##

[0414] General synthetic route for obtaining the naphthalimide dyes (A) according to the invention:

##STR00034##

Example 1Disulfide dye (A) for which R=n-C.sub.14H.sub.29
Example 2Disulfide dye (A) for which R=n-C.sub.16H.sub.33
Example 3Disulfide dye (A) for which R=n-C.sub.18H.sub.37

Example B: Disulfide Dyes Bearing a Hemicyanine/Styryl Chromophore of Formula (B) Below

[0415] ##STR00035##

[0416] General synthetic route for obtaining the hemicyanine or styryl dyes (B) according to the invention:

##STR00036##

with R.sup.1 and R.sup.2 representing a methyl group and R.sup.3 representing a linear or branched C.sub.1 to C.sub.22 hydrocarbon-based group, and X.sup., which may be identical or different, represent an anionic counterion, in particular a halide such as chloride or bromide,

[0417] This synthetic route allows the access to compounds (B) if 2-picoline is added in step ii):

##STR00037##

Example 4Disulfide dye (B) for which R.sup.3=n-C.sub.14H.sub.29
Example 5Disulfide dye (B) for which R.sup.3=n-C.sub.16H.sub.33
Example 6Disulfide dye (B) for which R.sup.3=n-C.sub.18H.sub.37
Example 7Disulfide dye (B) for which R.sup.3=n-C.sub.14H.sub.29
Example 8Disulfide dye (B) for which R.sup.3=n-C.sub.16H.sub.33
Example 9Disulfide dye (B) for which R.sup.3=n-C.sub.18H.sub.37

Dyes (A):

Example 1

[0418] This compound is synthesized in three steps according to the following reaction scheme:

##STR00038##

Example 1: 3,3-{Disulfanediylbis[ethane-2,1-diyl(1,3-dioxo-1H-benzo[de]isoquinoline-2,6(3H)-diyl)imino]}bis(N,N-dimethyl-N-tetradecylpropan-1-aminium) dibromide

Step 1: Synthesis of 6-chloro-2-(2-{[2-(6-chloro-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethyl]disulfanyl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione

[0419] ##STR00039##

Procedure:

[0420] 96.8 g of cystamine dihydrochloride (0.430 mol) and then 860 ml of a solution, prepared beforehand, containing 1 mol/l of potassium hydroxide (0.860 mol) in ethanol (48.16 g) are introduced into a 1.5 litre Pignat reactor equipped with a condenser, an argon or nitrogen inlet and a mechanical stirring system. The reaction medium is then brought to 50 C. and maintained at this temperature for 30 minutes. 200 g of 4-chloro-1,8-naphthalic anhydride (0.860 mol) are then added, using a powder funnel, and the medium is then maintained at the reflux point of ethanol for 8 hours while monitoring the reaction progress by TLC (60 F 254 plate): 9/1 dichloromethane/methanol eluent, UV revelation. The medium is then allowed to return to room temperature overnight. The reaction medium is then cooled in a bucket containing 2 litres of water+ice and is kept stirring for 2 hours. A beige-coloured precipitate is then obtained, which is filtered off on a sinter funnel and rinsed thoroughly with 1 litre of cold water. The precipitate is dried under vacuum at 40 C. in the presence of P.sub.2O.sub.5 to constant weight, to obtain the expected compound in the form of a beige-coloured powder. On the basis of the NMR and mass spectrometry, the chemical structure is in accordance with the expected product.

Step 2: Synthesis of 6-{[3-(dimethylamino)propyl]amino}-2-[2-({2-[6-{[3-(dimethylamino)propyl]amino}-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl]ethyl}disulfanyl)ethyl]-1H-benzo[de]isoquinoline-1,3(2H)-dione

[0421] ##STR00040##

Procedure:

[0422] 200 g of the compound synthesized in the preceding step 1 (0.344 mol) and 780 ml of N,N dimethyl-1,3-propanediamine (6.191 mol) are placed in a 2 litre four-necked flask equipped with a condenser, an argon inlet and a magnetic stirring system. The reaction medium is maintained at 110 C. with stirring for 8 hours, while monitoring the reaction progress by TLC (60 F 254 plate): 9/1 dichloromethane/methanol eluent, UV revelation. Once the reaction is complete, the medium is allowed to return to room temperature and is cooled in a beaker containing 3 litres of water+ice kept stirring for 2 hours at room temperature. The medium is then filtered through a sinter and then slurried twice with 21 litre of ethanol. After drying under vacuum in the presence of P.sub.2O.sub.5 at 40 C. to constant weight, orange-brown crystals are obtained. These crystals are taken up with vigorous stirring in 2 litres of hot isopropanol maintained at reflux for 4 hours. The medium is then hot-filtered (40 C.) through a No. 3 sinter and then dried in a vacuum oven to constant weight to obtain the expected product in the form of an orange-yellow powder. The mass spectrometry and NMR analyses are in accordance with the expected product.

Step 3: Synthesis of 3,3-{disulfanediylbis[ethane-2,1-diyl(1,3-dioxo-1H-benzo[de]isoquinoline-2,6(3H)-diyl)imino]}bis(N,N-dimethyl-N-tetradecylpropan-1-aminium) dibromide

[0423] ##STR00041##

Procedure:

[0424] 5 g of the compound synthesized in the preceding step 2 (0.007 mol) are placed in a 1 litre four-necked flask equipped with a condenser, an argon or nitrogen inlet and a magnetic stirring system. 25 g of bromotetradecane (0.09 mol) are then added, the reaction medium is maintained at 130 C. for 24 hours and then maintained at room temperature with stirring for 2 hours. The reaction medium is then filtered through a No. 3 sinter, and then rinsed with 100 ml of acetone. A precipitate is obtained in the form of a yellow powder which is in accordance with the expected product on the basis of the spectroscopic analyses.

[0425] By following the same process, and changing just the alkylating agent in the final step, the following compounds are obtained:

Example 2: 3,3-{Disulfanediylbis[ethane-2,1-diyl(1,3-dioxo-1H-benzo[de]isoquinoline-2,6(3H)-diyl)imino]}bis(N,N-dimethyl-N-hexadecylpropan-1-aminium) dibromide

[0426] ##STR00042##

Example 3: 3,3-{Disulfanediylbis[ethane-2,1-diyl(1,3-dioxo-1H-benzo[de]isoquinoline-2,6(3H)-diyl)imino]}bis(N,N-dimethyl-N-octadecylpropan-1-aminium) dibromide

[0427] ##STR00043##

Dyes (B:

Example 4: 1,1-{disulfanediylbis[ethane-2,1-diylimino(4-oxobutane-4,1-diyl)]}bis(4-{(2-[4-(dimethyltetradecylaminium)phenyl]ethenyl}pyridinium) tetrachloride

[0428] This compound is synthesized in three steps according to the following reaction scheme:

##STR00044##

With X.sup., identical or different, which represents Cl.sup. or Br.sup. or a mixture of Cl.sup. and Br.sup..

Step a): Synthesis of compound 1N,N-(disulfanediyldiethane-2,1-diyl)bis(4-chlorobutanamide)

[0429] 100 g of 50% sodium hydroxide solution cooled to 0 C. are placed in a 1 litre four-necked flask equipped with a condenser, an argon or nitrogen inlet and a magnetic stirring system. A solution, prepared beforehand, of 69.9 g of cystamine hydrochloride dissolved in 150 ml of demineralized water is then added dropwise over 1 hour 30 minutes, so as to keep the temperature below 6 C. The reaction medium is then kept stirring for 1 hour at 5 C. 92.2 g of 4-chlorobutyryl chloride are then added dropwise, so as to keep the temperature below 5 C. Once the addition is complete, the reaction medium is allowed to return to room temperature. The reaction medium is then filtered through a sinter and the precipitate formed is washed with 3100 ml of water and then with 3100 ml of isopropanol and dried under vacuum at 40 C. to constant weight. The NMR analyses are in accordance with the expected compound 1.

Step b): Synthesis of compound 21,1-{disulfanediylbis[ethane-2,1-diylimino(4-oxobutane-4,1-diyl)]}bis(4-methylpyridinium) dichloride

[0430] 2.84 g of compound 1 (0.00785 mol) prepared in the preceding step a) are placed in a 100 ml three-necked flask equipped with a condenser, an argon or nitrogen inlet and a magnetic stirring system and 15 ml of ethanol are then added. 1.75 g of 4-picoline (0.0188 mol) are then added and the reaction mixture is refluxed for 10 hours. The reaction progress is monitored by chromatography (HPLC) until the synthesis of compound 2 is complete.

Step c): Synthesis of Example 41,1-{disulfanediylbis[ethane-2,1-diylimino(4-oxobutane-4,1-diyl)]}bis(4-{(2-[4-(dimethyltetradecylaminium)phenyl]ethenyl}pyridinium) tetrachloride

[0431] The aldehyde was synthesized according to the synthetic process described in the following scientific publication: Novel cationic gemini surfactants as corrosion inhibitors for carbon steel pipeline, M. A. Hegazy, M. Abdallah, H. Ahmed; Corrosion Science, Vol. 52, Issue 9, pages 2897-2904 (2010).

Step c) May be Performed in the Following Manner

[0432] 6.8 g of aldehyde (0.0161 mol) are placed in the reactor of step b) containing compound 2 synthesized in the preceding step b), followed by addition of 40 ml of ethanol at room temperature. The reaction medium is then cooled to 0 C., followed by addition of a solution, prepared beforehand, of pyrrolidine acetate (by adding dropwise, at 0 C., 3.9 g of acetic acid to a solution of 3.3 g of pyrrolidine in 10 ml of ethanol). Once the addition is complete, the reaction medium is maintained at 5 C. for 1 hour and is then allowed to return to room temperature and is maintained at this temperature for 24 hours. The reaction progress is monitored by thin-layer chromatography (TLC). 50 ml of ethanol and then 250 ml of isopropanol are then added to the reaction medium with stirring at 5 C.

[0433] The precipitate formed is then filtered off and purified on a column of reverse-phase silica using a polar solvent in the presence of hydrochloric acid.

[0434] By following the same process, and just changing for an aldehyde bearing an amino group followed by alkylation in the final step, the following compounds are obtained:

Example 5: 1,1-{disulfanediylbis[ethane-2,1-diylimino(4-oxobutane-4,1-diyl)]}bis{4-[(2-(4-{[3-(dimethyl) 3-(hexadecyl)aminium)propyl]amino}phenyl)ethenyl]pyridinium}tetrachloride

[0435] ##STR00045## ##STR00046##

[0436] With X.sup., identical or different, which represents Cl.sup. or Br.sup. or a mixture of Cl.sup. and Br.sup..

Example 6: 1,1-{disulfanediylbis[ethane-2,1-diylimino(4-oxobutane-4,1-diyl)]}bis{4-[(2-(4-{[3-(dimethyl)-3-(octadecyl)amino)propyl]aminium}phenyl)ethenyl]pyridinium}tetrachloride

[0437] ##STR00047## ##STR00048##

[0438] With X.sup., identical or different, which represents Cl.sup. or Br.sup. or a mixture of Cl.sup. and Br.sup..

Dye Compositions:

[0439] Dye compositions at 0.5% by mass were prepared as follows:

0.05 gram (g) of dye (A) (Example 1, 2 or 3) or (B) (Example 4, 5 or 6) is placed in a flask and 10 g of a solvent mixture are added, this mixture being constituted of:
benzyl alcohol (52%)95% ethanol (33%)PG 400 polyethylene glycol 400 (2.6%)water (12.4%) as mass percentages.

[0440] The tests are performed on 1 g of locks of grey hair containing 90% white hairs (90NW) and then on 2.7 g of various types of sensitized (bleached) locks.

[0441] The dye composition is then applied to the keratin fibres at room temperature, with a leave-on time of 30 minutes.

[0442] The three dyes of formula (A) below:

Example 1: 3,3-{disulfanediylbis[ethane-2,1-diyl(1,3-dioxo-1H-benzo[de]isoquinoline-2,6(3H)-diyl)imino]}bis(N,N-dimethyl-N-tetradecylpropan-1-aminium) dibromide,
Example 2: 3,3-{disulfanediylbis[ethane-2,1-diyl(1,3-dioxo-1H-benzo[de]isoquinoline-2,6(3H)-diyl)imino]}bis(N,N-dimethyl-N-hexadecylpropan-1-aminium) dibromide,
Example 3: 3,3-{disulfanediylbis[ethane-2,1-diyl(1,3-dioxo-1H-benzo[de]isoquinoline-2,6(3H)-diyl)imino]}bis(N,N-dimethyl-N-octadecylpropan-1-aminium) dibromide, are evaluated relative to a comparative dye not comprising any fatty chain (A):

##STR00049##

Results in the L*a*b*system

[0443] The colour of the locks was evaluated in the L*a*b* system, using a Minolta CM 3600D spectrocolorimeter, (Illuminant D65).

[0444] In this L*a*b* system, L* represents the lightness, a* indicates the green/red colour axis and b* indicates the blue/yellow colour axis. The higher the value of L, the lighter or less intense the colour. Conversely, the lower the value of L, the darker or more intense the colour. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.

[0445] The selectivity corresponds to the variation in colouring between the locks of natural hair containing 90% white (90NW) and then dyed and the permanent-waved white (AS20) and then dyed hairs, which is measured by (E) according to the following equation:

E={square root over ((L*L.sub.o*).sup.2+(a*a.sub.0*).sup.2+(b*b.sub.0*).sup.2)}

[0446] In this equation, L*, a* and b* represent the values measured after dyeing of the permanent-waved hair AS20, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured after dyeing of the 90NW hair.

[0447] The smaller the selectivity value, the better the homogeneity of the colour between the root and the end of the hairs.

[0448] The chromaticity is calculated according to the following formula:

C*={square root over ((a*).sup.2+(b*).sup.2)}

[0449] The higher the value of the chromaticity C*, the more chromatic the colour of the treated keratin fibres.

Treatment

[0450] The locks are treated according to four procedures: [0451] a placebo protocol without straightening [0452] a protocol with straightening using a standard iron [0453] a protocol with straightening using a steampod: steam iron.

[0454] Two locks are prepared for each protocol: one is kept at 1 shampoo wash and the other is subjected to persistence at 10 shampoo washes. Thus, eight locks are treated for each dye chosen from Examples 1, 2, 3 or (A).

[0455] Each dye chosen from Examples 1, 2, 3 and (A) is dissolved at 0.5% by mass in the solvent mixture described previously: it is observed that the solution of Example 1 is slightly darker than those of Examples 2 or 3.

[0456] The solutions are applied to 90NW or AS20 locks according to the following protocol: [0457] wet the 1 g lock by treating five times with water at 37 C.; and then [0458] place it in a glass spout; [0459] next, add 2 g of dye solution at 0.5% by mass and then apply to the lock for 20 minutes at room temperature (RT); [0460] wring the lock dry;

[0461] Perform Brazilian straightening according to the following protocol: [0462] comb the lock; [0463] blow-dry five times on setting 2 of the hair dryer with a medium-diameter round brush; [0464] optionally, depending on the protocol, treat 10 times with a straightening iron using a comb (or steampod with or without steam); [0465] wash with a mild shampoo; and [0466] dry flat.

[0467] The locks treated with Examples 1 to 3 have a more pronounced yellow colour than that of (A), irrespective of the type of lock treated.

Study of the Dye of Example 2 on Various Types of Hair

[0468] The locks of hair were treated with the following compounds:

[0469] The tests are performed on two types of hair: [0470] natural Caucasian hair containing 90% natural white hairs (90NW); [0471] medium bleached Caucasian hair of alkaline solubility 20 (AS20).

Visual Observation

[0472] The visual observation shows that after treatment on the 90NW or AS hair, all the locks have a chromatic yellow colouring, which does not vary significantly after 5 and 10 shampoo washes. This is corroborated by the colorimetric measurements.

Comparison of the Intensity on Natural White Hairs:

[0473]

TABLE-US-00001 Process according Process with to the invention L* comparative L* 5% Example 2 + 43.97 5% Example (A' ) + 54.44 blow-drying + iron blow-drying + iron 210 C. + 1 sh. wash 210 C. + 1 sh. wash 5% Example 2 + 55.62 5% Example (A') + 59.9 blow-drying + iron blow-drying + iron 210 C. + 5 sh. washes 210 C. + 5 sh. washes 5% Example 2 + 55.67 5% Example (A') + 58.53 steampod + steampod + 1 sh. wash 1 sh. wash 5% Example 2 + 53.22 5% Example (A') + 61.45 steampod + steampod + 10 sh. washes 10 sh. washes

Comparison of the Intensity on AS20 Hair:

[0474]

TABLE-US-00002 Process according Process with to the invention L* comparative L* 5% Example 2 + 56.59 5% Example (A') + 60.04 steampod + 1 sh. wash steampod + 1 sh. wash 5% Example 2 + 57.88 5% Example (A') + 59.09 steampod + 10 sh. washes steampod + 10 sh. washes

Comparison of the Chromaticity on AS20 Hair:

[0475]

TABLE-US-00003 Process according to the Process with invention a* b* C* comparative a* b* C* 5% Example 2 + 6.94 40.73 41.31 5% Example (A) + 3.46 39.65 39.80 room temperature RT + 1 sh. wash (RT) + 1 sh. wash 5% Example 2 + 6.44 37.71 38.25 5% Example (A) + 3.95 36.59 36.80 RT + 5 sh. washes RT + 5 sh. washes

Comparison of the Selectivity at 10 Shampoo Washes Between AS20 Bleached Hair and 90NW Natural Hair:

[0476]

TABLE-US-00004 Process according Process with to the invention E comparative E 5% Example 2 11.49 5% Example 15.4 at RT + (A') at RT + 10 sh. washes 10 sh. washes

[0477] It is seen that the aliphatic chain borne by the dye of the invention makes it possible to significantly reduce the selectivity of the colouring between the root and the end, even after 10 shampoo washes, while at the same time improving the intensity of the colouring and the chromaticity.

Persistence StudyColorimetric Measurements of the Colour Build-Up E

[0478] One lock was treated for each dye, and the colour was then measured by spectrocolorimetry after 5 and 10 shampoo washes. The colour of a 90NW lock without treatment was also measured so as to have a reference. The colour differences were then calculated relative to the control lock without treatment.

[0479] The variation in colouring between the locks of dyed and washed hair and the undyed hair is measured by (E) according to the following equation:

E={square root over ((L*L.sub.o*).sup.2+(a*a.sub.0*).sup.2+(b*b.sub.0*).sup.2)}

[0480] In this equation, L*, a* and b* represent the values measured after dyeing and shampooing, and L.sub.0*, a.sub.0* and b.sub.0* represent the values measured before dyeing.

[0481] Results of the spectrocolorimetric measurements for the various Examples 1 (C14), 2 (C16) and 3 (C18) relative to the control (lock without treatment):

[0482] First, it is seen that the build-up of the colour is very good for Example 1, 2 or 3 of the invention. The decrease in colour is virtually non-existent after five shampoo washes and particularly small after 10 shampoo washes, which demonstrates the efficient colour persistence on shampooing of the hair with the dyes of the invention.

[0483] Specifically, after 10 shampoo washes, Examples 1 to 3 of the invention clearly show a coating effect of the treated lock in comparison with the control lock. There is virtually no difference between the three examples of the invention.

Durability Study

[0484] In order to study the durability of the care effect that may be afforded by the dyes of the invention, tests are performed on various types of hair of different sensitivity and curliness. Thus, bleached type II locks were treated with Example 2 according to the protocols with straightening using an iron and using a steampod, and were then subjected to shampooing so as to evaluate the long-term persistence of the care active agent. From the visual and L*a*b spectrocolorimetry results, it is seen that the colouring is very persistent when the keratin fibres are treated with the dye of Example 2 according to the invention in the presence of an iron (standard or steam iron).

[0485] It is also seen that the dyes of the invention (Example 2) make it possible to obtain keratin fibre colourings with very good care persistence afforded to degraded keratin fibres (AS2).

Sensory Evaluation

Evaluation Score:

[0486]

TABLE-US-00005 Effects Process Process evaluated on using a using a steam hair after straightening iron of steampod treatment with iron + type + example 2 40 sh. washes 40 sh. Washes Softness 4 4 Coating 3 4 Persistence 4 4 Sheen 3 3 Manageability 4 4 Disentangling 4 4

[0487] The results of the sensory evaluation (evaluated by a score ranging from 1 to 4 with 1 being the poorest score and 4 the best) corroborate the visual observations and the spectroscopic colour measurements: the care effect is persistent even after 40 shampoo washes.

[0488] It is seen from this evaluation that the process which uses the step with a steam iron of steampod type is better than the process using a standard straightening iron.