Patent Application
20070010663
The present disclosure relates to dissymmetrical cationic diazo compounds having at least one 2-imidazolium unit and a cationic or non-cationic linker, to dyeing compositions comprising such compounds as a direct dye in a medium appropriate for the dyeing of keratin fibers, to a method of coloring keratin fibers that employs this composition, and to a device having a plurality of compartments.
It is known practice to dye keratin fibers, including human keratin fibers such as the hair, with dyeing compositions containing direct dyes. These compounds are colored, and coloring, molecules having an affinity for the fibers. It is known practice, for example, to use direct dyes of nitrobenzene type, anthraquinone dyes, nitropyridines and dyes of azo, xanthene, acridine, azine or triarylmethane type.
Commonly these dyes are applied to the fibers, optionally in the presence of an oxidizing agent if a simultaneous fiber lightening effect is desired. When the leave-in time has elapsed, the fibers are rinsed, optionally washed, and dried.
The colorations which result from the use of direct dyes are temporary or semi-permanent colorations, because the nature of the interactions which bind the direct dyes to the keratin fiber, and their desorption from the surface and/or the core of the fiber, are responsible for their relatively low tinctorial strength and relatively poor wash resistance or perspiration resistance.
It is known from European Patent Application No. EP 1377263 to employ particular direct cationic diazo dyes containing two cationic heterocyclic groups. These compounds, although representing an advance in the art, give dyeing results which nevertheless remain capable of improvement.
For the purposes of the present disclosure, and in the absence of any indication otherwise:
The compounds according to the present disclosure are termed “dissymmetrical” when there is no plane of symmetry perpendicular to the linker L. In other words, the two formula members on either side of the linker L are different. More specifically, they are different when their substituents differ in terms of their identities and/or their positions in the molecule.
Where the different groups forming part of the structure of the compounds according to the present disclosure are substituted, the skilled person will select them such that the dissymmetry of the molecule is respected.
One aspect of the present disclosure relates to direct dyes which do not exhibit one or more of the drawbacks of existing direct dyes.
The present disclosure accordingly provides dissymmetrical cationic diazo compounds represented by formulae (I), (II), (III) and (IV) below, their resonance forms, and their acid addition salts and/or their solvates, wherein in the compounds of formulae (I), (II), (III) and (IV), the formula members attached to each side of the linker L are either compositionally different or positionally different such that the compounds as a whole are dissymmetrical:
in which formulae:
The present disclosure also relates to dyeing compositions comprising such compounds of structure (I), (II), (III) and (IV), or their addition salts with an acid, as direct dyes in a medium appropriate for the dyeing of keratin fibers.
A further aspect of the present disclosure relates to a method of coloring keratin fibers which comprises contacting a composition according to the present disclosure with said fibers, which are dry or wet, for a time sufficient to give a desired effect, i.e., desired color.
The present disclosure also relates to a device having a plurality of compartments, i.e., a multi-compartment device, and containing in a first compartment the composition according to the present disclosure and in a second compartment an oxidizing composition.
It has been found that the compounds of formula (I) as defined above may exhibit effective resistance to external agents such as, for example, shampoos, and may do so even when the keratin fiber is sensitized. Furthermore, these compounds may exhibit improved dyeing properties, such as the chromaticity, the coloring power, and/or a low selectivity, which is to say that the compounds of the present disclosure may allow colorations to be obtained which are more uniform between the end and the root of the hair.
Other characteristics and advantages of the present disclosure, however, will appear more clearly from reading the description and the examples presented hereinbelow.
In the text below, and in the absence of any indication otherwise, the end-points delimiting a range of values are included in that range.
As indicated above, the present disclosure relates to compounds corresponding to the formulae (I), (II), (III) and (IV), their salts and/or solvates.
In one embodiment, the compounds of formulae (I), (II), (Ill) and (IV) according to the present disclosure are such that the identical or different radicals R1 independently of one another may be chosen from:
According to one embodiment, the identical or different groups R1 may be chosen from methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl and benzyl radicals.
The compounds of formula (I), (II), (III) and (IV) according to the present disclosure may be such that the radicals R2, which are identical or different, independently of one another may be chosen from:
According to one embodiment, the identical or different radicals R2 from formulae (I), (II), (III) and (IV) independently of one another may be chosen from methyl, ethyl, 2-hydroxyethyl, 2-methoxyethyl, methylsulphonyl (CH3SO2—), methylcarbonylamino (CH3CONH—), hydroxyl, amino, methylamino, dimethylamino, 2-hydroxyethylamino, methoxy, ethoxy and phenyl radicals.
According to a further embodiment, the two radicals R2 from formulae (I), (II), (III) and (IV) may optionally form, with the carbon atoms to which they are attached, a secondary, 6-membered aromatic ring optionally substituted by at least one identical or different group chosen from hydroxyl, C1-C4 alkyl, C1-C4 alkoxy, amino, and amino substituted by one or two identical or different C1-C4 alkyl radicals which optionally carry at least one hydroxyl or methylcarbonylamino group.
In accordance with this further embodiment, the two radicals R2 may optionally form, with the carbon atoms to which they are attached, a secondary, 6-membered aromatic ring optionally substituted by at least one identical or different group chosen from hydroxyl, methoxy, ethoxy, amino, 2-hydroxyethylamino, dimethylamino and (di)-2-hydroxyethylamino.
According to at least one embodiment, the coefficient e is 0.
According to an embodiment of the present disclosure, the radicals R3 of the formulae (I), (II), (III) and (IV), which are identical or different, independently of one another may be chosen from:
In at least one embodiment the radicals R3, which are identical or different, independently of one another, may be chosen from:
According to this embodiment, the radicals R3, which are identical or different, independently of one another, may be chosen from, for example:
According to a further embodiment, when the coefficient m′ is greater than or equal to 2, two adjacent radicals R3 may form, with the carbon atoms to which they are attached, a secondary, 6-membered aromatic ring optionally substituted by one or more identical or different groups chosen from hydroxyl groups, —NR4—Ph, —NR4—Ph—NR5R6 and —NR4—Ph—OR7 groups, C1-C4 alkyl groups, C1-C4 alkoxy groups, C2-C4 (poly)hydroxyalkoxy groups, C1-C4 alkylcarbonylamino groups, amino groups, and amino groups substituted by one or two identical or different C1-C4 alkyl radicals which optionally carry at least one hydroxyl group.
According to this embodiment, two adjacent radicals R3 may form, with the carbon atoms to which they are attached, a secondary, 6-membered aromatic ring which is optionally substituted by one or more identical or different groups chosen from hydroxyl, methoxy, ethoxy, 2-hydroxyethyloxy, amino, methylcarbonylamino, (di)-2-hydroxyethylamino, —NH—Ph, —NH—Ph—NH2, —NH—Ph—NHCOCH3, —NH—Ph—OH and —NH—Ph—OCH3 groups.
With regard to the radicals R4 and R7, these radicals may be chosen from:
In accordance with one embodiment of the present disclosure, the radicals R4 and R7 may be chosen from:
With regard to the radicals R5 and R6, independently of one another, these identical or different radicals may be chosen from, for example:
In accordance with one embodiment of the invention, the radicals R5 and R6, which are identical or different, independently of one another may be chosen from, for example:
In a further embodiment, the radicals R5 and R6, which are identical or different, independently of one another, may be chosen from:
In at least embodiment of the present disclosure, the radicals R5 and R6 form, together with the nitrogen atom to which each is attached, a heterocycle containing 1 to 3 heteroatoms, such as, for example, 1 or 2 heteroatoms, chosen from N, O and S, such as, for example, N, and containing 5 to 7 ring members, which is saturated or unsaturated, aromatic or non-aromatic, and is optionally substituted.
The heterocycle containing 5 to 7 ring members may be chosen from, for example, the following heterocycles: piperidine, 2-(2-hydroxyethylpiperidine), 4-(aminomethyl)piperidine, 4-(2-hydroxyethyl)piperidine, 4-(dimethylamino)piperidine, piperazine, 1-methylpiperazine, 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, 1-hydroxyethylethoxypiperazine, homopiperazine, 1-methyl-1,4-perhydrodiazepine, pyrrole, 1,4-dimethylpyrrole, 1-methyl-4-ethylpyrrole, and 1-methyl-4-propylpyrrole.
In at least one embodiment, the heterocycle containing 5 to 7 ring members may also be chosen from a heterocycle of piperidine, piperazine, homopiperazine, pyrrole, imidazole or pyrazole type which is optionally substituted by one or more identical or different methyl, hydroxyl, amino and/or (di)methylamino radicals.
According to another embodiment, the radicals R5 and R6 may form, with the carbon atom of the aromatic ring optionally substituted by a hydroxyl and adjacent to that to which —NR5R6 is attached, a 5- or 6-membered saturated heterocycle.
For example, the group —NR5R6 with the aromatic nucleus optionally substituted by a hydroxyl may correspond to the following compounds:
In a first embodiment, L is a non-cationic linker.
According to this embodiment, non-cationic linker L connecting the two different azo chromophores may be chosen from:
According to a second embodiment, the linker L is cationic.
According to this embodiment, cationic linker L connecting the two different azo chromophores may be chosen from:
Among non-cationic alkyl-type linkers L that may be used according to the present disclosure, non-limiting mention may be made of methylene, ethylene, linear or branched propylene, linear or branched butylene, linear or branched pentylene, and linear or branched hexylene radicals which are optionally substituted and/or interrupted as indicated above.
These identical or different substituents may be chosen from, for example, hydroxyl, C1-C2 alkoxy, C1-C2 dialkylamino, (C1-C4 alkyl)carbonyl and C1-C4 alkyl sulphonyl.
Examples of an aromatic or non-aromatic, saturated or unsaturated cycle or heterocycle interrupting the alkyl radical of the linker L include phenylene, naphthylene, phenanthrylene, triazinyl, pyrimidinyl, pyridinyl, pyridazinyl, quinoxalinyl and cyclohexyl radicals.
Further examples of linkers L include methylene, ethylene, linear or branched propylene, linear or branched butylene, linear or branched pentylene and linear or branched hexylene radicals optionally substituted and/or interrupted as indicated above.
Examples of an aromatic or non-aromatic, saturated or unsaturated cycle or heterocycle interrupting the alkyl radical of the linker L include phenylene or naphthylene, phenanthrylene, triazinyl, pyrimidinyl, pyridinyl, pyridazinyl, quinoxalinyl and cyclohexyl radicals.
Among radicals L that can be used according to an embodiment of the present disclosure, non-limiting mention may be made of the following radicals L:
In these formulae:
Examples of radicals L may also include:
Among cationic linker L radicals that may be used according to the present disclosure, non-limiting mention may be made of a C2-C20 alkyl radical:
1—interrupted by at least one group corresponding to the following formulae:
wherein:
According to one embodiment of formulae (a) and (d), R9 and R10, separately, are chosen from, for example, C1-C6 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C2-C4 polyhydroxyalkyl radicals, C1-C6 alkoxy-C2-C4 alkyl radicals and C2-C6 dimethylaminoalkyl radicals.
In a further embodiment, R9 and R10 separately are chosen from methyl, ethyl and 2-hydroxyethyl radicals.
According to one embodiment of formulae (b) and (c), R13 is chosen from halogen atoms chosen from chlorine and fluorine, C1-C6 alkyl radicals, C1-C4 monohydroxyalkyl radicals, C1-C4 alkoxy radicals, hydroxycarbonyl radicals, C1-C6 alkylthio radicals and amino radicals disubstituted by a C1-C4 alkyl radical.
According to at least one embodiment of formulae (b) and (c), R13 is chosen from a chlorine atoms and methyl, ethyl, 2-hydroxyethyl, methoxy, hydroxycarbonyl and dimethylamino radicals.
According to a further embodiment of formulae (b) and (c), z is 0.
In the formulae of the compounds of formulae (I), (II), (III) and (IV), An is chosen from an organic anion, an inorganic anion and an anion mixture allowing the charge or charges on the compounds of formula (I), (II), (III) and (IV) to be balanced, and chosen from, for example, a halide such as chloride, bromide, fluoride or iodide; a hydroxide; a sulphate; a hydrogensulphate; an alkylsulphate for which the linear or branched alkyl moiety is C1-C6, such as the methylsulphate or ethylsulphate ion; carbonates and hydrogencarbonates; salts of carboxylic acids, such as formate, acetate, citrate, tartrate and oxalate; alkylsulphonates for which the linear or branched alkyl moiety is C1-C6, such as the methylsulphonate ion; arylsulphonates for which the aryl moiety, such as phenyl, is optionally substituted by one or more C1-C4 radicals, such as 4-tolylsulphonate, for example; and alkylsulphonyls such as mesylate.
The acid addition salts of the compounds of formulae (I), (II), (III) and (IV) may be, by way of example, the addition salts with an organic or inorganic acid such as hydrochloric acid, hydrobromic acid, sulphuric acid or alkyl- or phenyl-sulphonic acids such as p-toluenesulphonic acid or methylsulphonic acid.
The solvates of compounds of formulae (I), (II), (III) and (IV) may be chosen from the hydrates of such compounds and the combination of a compound of formula (I), (II), (III) and (IV) with a linear or branched C1-C4 alcohol such as methanol, ethanol, isopropanol or n-propanol.
In accordance with one embodiment of the present disclosure, the compounds correspond to formulae (I′), (I″), (I′″), (II′), (II″), (II′″), (III′), (III″), (III′″), (IV′), (IV″), (IV′″) below, and also to their resonance forms and/or their acid addition salts and/or their solvates:
where R1, R3, W1 and m′ are as defined above.
where R1, R3, W1 and m′ are as defined above.
The compounds corresponding to the monoazo species may be obtained from preparation processes described, for example, in the documents U.S. Pat. No. 5,708,151, J. Chem. Res., Synop. (1998), (10), 648-9, U.S. Pat. No. 3,151,106, U.S. Pat. No. 5,852,179, Heterocycles, 1987, 26 (2) 313-7, Synth. Commun. 1999, 29 (13), 2271 -6, Tetrahedron, 1983, 39 (7), 1091-1101. As for the diazo compounds, reference may be made to European Patent Application No. EP 1377263 for a synthesis description.
The present disclosure further relates to a dyeing composition comprising at least one compound of formula (I), (II), (III) and/or (IV), or its acid addition salts, as direct dye in a medium appropriate for the dyeing of keratin fibers.
The total concentration of compound(s) of formula (I), (II), (III) and/or (IV) may range from 0.001% to 20% by weight relative to the total weight of the dyeing composition, such as from 0.01% to 10% by weight or from 0.05% to 5% by weight.
The dyeing composition according to the present disclosure may also comprise at least one oxidation base. This oxidation base may be chosen from the oxidation bases conventionally used in oxidation dyeing, such as, for example, para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the para-phenylenediamines that may be used according to at least one embodiment of the present disclosure, non-limiting mention may be made, for example, of para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxy-ethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-amino-phenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene, and the acid addition salts thereof.
Among the para-phenylenediamines mentioned above, para-phenylenediamines chosen from para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine, and the acid addition salts thereof may be used in at least one embodiment.
Among the bis(phenyl)alkylenediamines that may be used according to the present disclosure, non-limiting mention may be made, for example, of N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-amino-phenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(4-methyl-aminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4+-amino-3′-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the acid addition salts thereof.
Among the para-aminophenols that may be used according to the present disclosure, non-limiting mention may be made, for example, of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylamino-methyl)phenol and 4-amino-2-fluorophenol, and the acid addition salts thereof.
Among the ortho-aminophenols that may be used according to the present disclosure, non-limiting mention may be made, for example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the acid addition salts thereof.
Among the heterocyclic bases that may be used according to the present disclosure, non-limiting mention may be made, for example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Among the pyridine derivatives that may be used according to the present disclosure, non-limiting mention may made of the compounds described, for example, in British Patent Nos. GB 1 026 978 and GB 1 153 196, as well as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine, and the acid addition salts thereof.
Among the pyrimidine derivatives that may be used according to the present disclosure, non-limiting mention may be made of the compounds described, for example, in Patent Nos. DE 2 359 399; JP 88-169 571; JP 05-163124; EP 0 770 375 or International Patent Application No. WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-amino-pyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo-[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine and 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine, and the acid addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists.
Among the pyrazole derivatives that may be used according to the present disclosure, non-limiting mention may be made of the compounds described in Patent Nos. DE 3 843 892 and DE 4 133 957 and Patent Application Nos. WO 94/08969, WO 94/08970, FR 2 733 749 A and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the acid addition salts thereof.
The dyeing composition according to the present disclosure may also contain one or more couplers conventionally used for dyeing keratin fibers. Among these couplers, non-limiting mention may be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers.
Examples that may also be mentioned include 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene and 2,6-bis(β-hydroxy-ethylamino)toluene and the acid addition salts thereof.
In the dyeing composition of the present disclosure the oxidation base or bases may be present in a total amount ranging from 0.001% to 10% by weight relative to the total weight of the dyeing composition, such as, for example, from 0.005% to 6% by weight.
The coupler or couplers may be present in a total amount ranging from 0.001% to 10% by weight relative to the total weight of the dyeing composition, such as, for example, from 0.005% to 6% by weight.
The acid addition salts that may be used in the context of the dyeing compositions of the present disclosure for the oxidation bases and couplers may be chosen from those listed in the context of the definition of the compounds of formula (I), (II), (III) and (IV).
The composition according to the present disclosure may optionally comprise at least one additional direct dye other than the compounds of formula (I), (II), (III) and (IV). This at least one additional direct dye may be chosen from cationic and nonionic species.
Non-limiting examples that may be mentioned include nitrobenzene dyes, azo, azomethine, methine, tetraazapentamethine, anthraquinone, naphthoquinone, benzoquinone, phenothiazine, indigoid, xanthene, phenanthridine and phthalocyanine dyes, dyes derived from triarylmethane, and natural dyes, alone or as mixtures.
The at least one additional direct dye may be chosen from, for example, the following red and orange nitrobenzene dyes:
The at least one additional direct dye may also be chosen from yellow and green-yellow nitrobenzene direct dyes; non-limiting mention may be made, for example, of the compounds chosen from:
Mention may also be made of blue and violet nitrobenzene direct dyes; for instance:
Among the azo direct dyes that may be used according to the present disclosure, non-limiting mention may be made of the cationic azo dyes described in Patent Application Nos. WO 95/15144, WO 95/01772 and EP 714954, FR 2 822 696, FR 2 825 702, FR 2 825 625, FR 2 822 698, FR 2 822 693, FR 2 822 694, FR 2 829 926, FR 2 807 650, WO 02/078660, WO 02/100834, WO 02/100369 and FR 2 844 269.
Among the azo direct dyes that may be used according to the present disclosure, non-limiting mention may be made of the following dyes:
1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-imidazolium chloride;
1,3-dimethyl-2-[(4-aminophenyl)azo]-1H-imidazolium chloride; and
1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium methylsulphate.
Among the azo direct dyes that may also be mentioned are the following dyes described in the Color Index International 3rd edition:
Disperse Red 17;
Acid Yellow 9;
Acid Black 1;
Basic Red 22;
Basic Red 76;
Basic Yellow 57;
Basic Brown 16;
Acid Yellow 36;
Acid Orange 7;
Acid Red 33;
Acid Red 35;
Basic Brown 17;
Acid Yellow 23;
Acid Orange 24; and
Disperse Black 9.
Non-limiting mention may also be made of 1-(4′-aminodiphenylazo)-2-methyl-4-[bis(p-hydroxyethyl)amino]benzene and 4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulphonic acid.
Among the quinone direct dyes that may be used according to the present disclosure, non-limiting mention may be made of the following dyes:
Disperse Red 15;
Solvent Violet 13;
Acid Violet 43;
Disperse Violet 1;
Disperse Violet 4;
Disperse Blue 1;
Disperse Violet 8;
Disperse Blue 3;
Disperse Red 11;
Acid Blue 62;
Disperse Blue 7;
Basic Blue 22;
Disperse Violet 15;
Basic Blue 99;
and also the following compounds:
1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone;
1-aminopropylamino-4-methylaminoanthra-quinone;
1-aminopropylaminoanthraquinone;
5-β-hydroxyethyl-1,4-diaminoanthraquinone;
2-aminoethylaminoanthraquinone; and
1,4-bis(β,γ-dihydroxypropylamino)anthraquinone.
Among the azine dyes that may be used according to the present disclosure, non-limiting mention may be made of the following compounds:
Basic Blue 17; and
Basic Red 2.
Among the triarylmethane dyes that may be used according to the present disclosure, non-limiting mention may be made of the following compounds:
Basic Green 1;
Acid Blue 9;
Basic Violet 3;
Basic Violet 14;
Basic Blue 7;
Acid Violet 49;
Basic Blue 26; and
Acid Blue 7.
Among the indoamine dyes that may be used according to the present disclosure, non-limiting mention may be made of the following compounds:
2-β-hydroxyethylamino-5-[bis(β-4′-hydroxyethyl)amino]anilino-1,4-benzoquinone;
2-β-hydroxyethylamino-5-(2′-methoxy-4′-amino)anilino-1,4-benzoquinone;
3-N-(2′-chloro-4′-hydroxy)phenylacetyl-amino-6-methoxy-1,4-benzoquinoneimine;
3-N-(3′-chloro-4′-methylamino)phenylureido-6-methyl-1,4-benzoquinoneimine; and
3-[4′-N-(ethylcarbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoquinoneimine.
Among the dyes of tetraazapentamethine type that may be used according to the present disclosure, non-limiting mention may be made of the following compounds given in the table below, with An being defined as above:
Among the natural direct dyes that may be used according to the present disclosure, non-limiting mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenidin. Extracts or decoctions containing these natural dyes may also be used, such as, for example, henna-based poultices and extracts.
When they are present, the amount of additional direct dye in the composition may range from 0.001% to 20% by weight relative to the total weight of the composition, such as from 0.01% to 10% by weight relative to the total weight of the composition.
The medium that is suitable for dyeing, also known as the dye vehicle, generally comprises water or a mixture of water and at least one organic solvent to dissolve the compounds that would not be sufficiently water-soluble.
In one embodiment, the organic solvents may be chosen from, for example, linear or branched saturated monoalcohols or diols containing 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycols or glycol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol and its ethers, for instance propylene glycol monomethyl ether, butylene glycol and dipropylene glycol; and also diethylene glycol alkyl ethers, such as the C1-C4 ethers, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
The solvents described above, when they are present, may be present in an amount ranging from 1% to 40% by weight, for example, from 5% to 30% by weight, relative to the total weight of the composition.
The dyeing composition in accordance with the present disclosure may also include various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance silicones, which may or may not be volatile or be modified, film-forming agents, ceramides, preservatives and opacifiers.
The adjuvants may be present individually in an amount ranging from 0.01% to 20% by weight relative to the total weight of the composition.
The person skilled in the art will of course take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dyeing composition in accordance with the present disclosure are not, or not substantially, adversely affected by the envisaged addition.
The pH of the dyeing composition in accordance with the present disclosure may range from about 3 to 12, such as, for example, from about 5 and 11. The pH may be adjusted to the desired value using acidifying or alkalifying agents usually used in the dyeing of keratin fibers, or alternatively using standard buffer systems.
Among the acidifying agents that may be mentioned, for example, are mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Among the alkalifying agents that may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds having the following formula:
wherein W is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which are identical or different, are chosen from hydrogen atoms, C1-C4 alkyl radicals and C1-C4 hydroxyalkyl radicals.
The dyeing composition according to the present disclosure may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibers, such as human hair.
The composition according to the present disclosure may further comprise at least one oxidizing agent. When the composition comprises at least one oxidizing agent, the composition is referred to as a ready-to-use composition.
For the purposes of the present disclosure, a ready-to-use composition is a composition intended to be applied immediately to the keratin fibers, i.e., it may be stored in unmodified form before use or may result from the extemporaneous mixing of two or more compositions.
The composition may also be obtained by mixing the composition with an oxidizing composition.
The at least one oxidizing agent may be any oxidizing agent conventionally used in the field. Thus it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases. In at least one embodiment, hydrogen peroxide may be used as the oxidizing agent.
The amount of the at least one oxidizing agent may range from 1% to 40% by weight relative to the total weight of the ready-to-use composition, such as, for example, from 1% to 20% by weight relative to the total weight of the ready-to-use composition.
The oxidizing composition used may be an aqueous composition and may be in the form of a solution or an emulsion.
In at least one embodiment, the composition free of oxidizing agent is mixed with about 0.5 to 10 weight equivalents of the oxidizing composition.
The pH of the ready-to-use composition may range from 4 to 12, such as, for example, from 7 to 11.5.
The pH of the composition may be adjusted using an acidifying or alkalifying agent chosen from those mentioned previously.
The present disclosure further relates to a method of coloring that comprises the application of a dyeing composition according to the present disclosure to wet or dry keratin fibers.
The application to the fibers of the dyeing composition comprising the compound(s) of formula (I), (II), (III) and/or (IV) or the acid addition salts thereof, optionally at least one oxidation base optionally combined with at least one coupler, and optionally at least one additional direct dye, may be performed in the presence of an oxidizing agent.
This oxidizing agent may be added to the composition comprising the compound(s) of formula (I), (II), (III) and/or (IV) and the optional oxidation bases, couplers and/or additional direct dyes, either at the time of use or directly on the keratin fiber.
The oxidizing composition may also include various adjuvants conventionally used in compositions for dyeing the hair and as defined above.
The pH of the oxidizing composition containing the oxidizing agent may be such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers ranges from 4 to 12 approximately, such as, for example, from 7 to 11.5. The pH may be adjusted to the desired value by means of acidifying or alkalifying agents usually used in the dyeing of keratin fibers and as described above.
The composition that is finally applied to the keratin fibers may be in various forms, such as in the form of liquids, creams or gels or in any other form that is suitable for dyeing keratin fibers, such as human hair.
According to one embodiment, the composition according to the present disclosure is free of oxidation base and coupler.
The composition applied may optionally comprise at least one oxidizing agent.
The composition is thus applied to the wet or dry keratin fibers and is then left for a leave-in time that is sufficient to give the desired coloration.
Whatever the version adopted (with or without oxidizing agent), the leave-in time may range from a few seconds to one hour, such as, for example, from 3 to 30 minutes.
The temperature at which the composition acts may range from 15 to 220° C., such as, for example, from 15 to 80° C. or from 15 to 40° C.
After the leave-in time, the composition may be removed by rinsing with water, optionally followed by washing with a shampoo, and then optionally by drying.
Another aspect of the present disclosure relates to a device having a plurality of compartments, i.e., a multi-compartment device, or dyeing kit, in which a first compartment contains the dyeing composition of the invention and a second compartment contains the oxidizing composition. This device may be equipped with a means for delivering the desired mixture to the hair, such as the devices described in French Patent No. FR 2 586 913.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches. Also, where the term “between” is used, the ranges defined include the stated endpoints.
Notwithstanding the numerical ranges and parameters setting forth the broad scope of the invention as approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in its respective testing measurement.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
1—Synthesis of Compounds:
Compound 1 (1.477 g, n=0.002 mol) was reacted in the presence of 1.08 g (n=0.02 mol) of p-phenylenediamine in 20 ml of isopropanol at 110° C. for 8 hours. Concentration of the reaction mixture gave a violet residue. Purification was required by liquid chromatography to give the pure compound 2 in the form of a dark purple-red powder.
The 1H NMR and mass analyses were in accordance with the expected product.
Compound 3 is available commercially (Interchim).
Compound 5 was synthesized in 3 steps:
1.13 g of compound 3 were stirred at 85° C. for 8 hours in the presence of 3.86 ml of 1,6-dibromohexane in 80 ml of 1,2-dichloroethane. The reaction mixture was subsequently brought to ambient temperature. The reaction mixture was diluted with dichloromethane and washed with water. The organic phase was separated off, dried over sodium sulphate, filtered and concentrated under reduced pressure. This gave a dark violet powder (compound 4/4′, mixture of bromo compound and chloro compound).
The 1H NMR and mass analyses were in accordance with the expected product (mixture of bromo compound and chloro compound).
Step 2
4.38 g of compound (4/4′) were stirred at 100° C. for 22 hours in the presence of 1.9 g of compound 5 and 0.05 g of Kl in 15 ml of dimethylformamide. The reaction mixture was subsequently brought to ambient temperature and then poured into a mixture containing ethyl acetate and diisopropyl ether (proportion 3/7). A precipitate was formed. It was isolated by filtration. The solid obtained was dissolved in dichloromethane and the solution was then poured into a solution containing ethyl acetate and isopropanol (proportion 4/1). A further precipitate appeared. It was isolated by filtration and dried under vacuum. This gave a dark purple powder corresponding to the expected compound 6.
The 1H NMR and mass analyses were in accordance with the structure of the expected compound 6.
1 g of compound 6 and 0.87 ml of ethanolamine were reacted in 6 ml of pentanol and 1 ml of methanol at 95° C. for 5 hours. The reaction mixture was subsequently brought to ambient temperature and then poured into a mixture containing ethyl acetate and diisopropyl ether. A precipitate was formed. It was isolated by filtration and dried under vacuum. Purification by liquid chromatography gave a dark purple-red powder.
The 1H NMR and mass analyses were in accordance with the structure of the expected compound 7.
0.68 g of compound 6 and 0.37 ml of pyrrolidine were reacted in 8 ml of isopropanol at 67° C. for 24 hours. The reaction mixture was subsequently brought to ambient temperature and then poured into a mixture containing ethyl acetate and diisopropyl ether. A precipitate was formed. It was isolated by filtration and dried under vacuum. Purification by liquid chromatography gave a fuchsia-colored powder.
The 1H NMR and mass analyses were in accordance with the structure of the expected compound 8.
Compound 9 is commercial (Interchim).
Step 1:
Compound 9 (2.5 g) was reacted in the presence of 50 ml of 1,6-dibromohexane at 100° C. for 12 hours. The reaction mixture was brought to ambient temperature beforehand, water was added, and the product was then extracted with dichloromethane. Drying over sodium sulphate, filtration and evaporation gave a violet powder (2 g) corresponding to the compound of structure 10.
The 1H NMR and mass analyses were in accordance with the expected product.
Step 2:
Compound 10 (0.1 g) and 0.042 g of compound 5 were reacted in the presence of 1 ml of DMF at 60° C. for 7 days. The reaction mixture was brought to ambient temperature beforehand. The residue obtained by precipitation of the reaction mixture from diisopropyl ether was purified by liquid chromatography. A fuchsia powder corresponding to the compound of structure 11 was obtained.
The 1H NMR and mass analyses were in accordance with the expected product.
Compound 12 was obtained by reacting the diazonium salt of 3-aminopyridine with dimethylaniline.
Step 1:
Compound 12 (1 g) was reacted in the presence of 6.82 ml of 1,6-dibromohexane at 90° C. for 12 hours. The reaction mixture was brought to ambient temperature beforehand and then poured into a solution containing diisopropyl ether. A precipitate was obtained and was then isolated by filtration and dried. This gave a dark orange-colored powder (2 g) corresponding to the compound of expected structure 13.
The 1H NMR and mass analyses were in accordance with the expected product.
Step 2:
Compound 13 (1 g) and 0.5 g of compound 5 were reacted in the presence of 10 ml of DMF at 90° C. for 2 days. The reaction mixture was brought to ambient temperature beforehand. The residue obtained by precipitating the reaction mixture from diisopropyl ether was purified by liquid chromatography. An orange-yellow powder corresponding to the compound of structure 14 was obtained.
The 1H NMR and mass analyses were in accordance with the expected product.
In a three-necked flask with a top-mounted condenser, compound 5 (0.216 g, 1 mmol) was stirred at ambient temperature for 48 hours in the presence of 2 ml of 1,5-dibromopentane in 5 ml of acetonitrile.
Following reaction, the reaction mixture was concentrated. The residue obtained was purified by flash silica chromatography. 208 mg of an orange-yellow powder corresponding to compound 15 were obtained.
The analyses were in accordance with the expected product.
Compound 16 was obtained by reacting the diazonium salt of p-anisidine with imidazole.
In a three-necked flask with a top-mounted condenser, compound 15 (0.223 g, 0.5 mmol), compound 16 (0.121 mg, 0.6 mmol) and sodium hydroxide (0.025 g; 0.625 mmol) were stirred at ambient temperature for 48 hours in the presence of 50 ml of water and 4 ml of toluene.
After reaction, the reaction mixture was concentrated. The residue obtained was washed a number of times with toluene. 240 mg of an orange-yellow powder corresponding to compound 17 were obtained.
The analyses were in accordance with the expected product.
In a three-necked flask with a top-mounted condenser, compound 17 (0.283 g, 0.5 mmol) and pyrrolidine (0.043 g; 0.6 mmol) were stirred at 80° C. for 4 hours in the presence of 10 ml of isopropanol.
After reaction, the reaction mixture was concentrated. The residue obtained was purified by flash silica chromatography. 113 mg of a fuchsia-red powder corresponding to compound 18 were obtained.
The analyses were in accordance with the expected product.
In a three-necked flask with a top-mounted condenser, compound 18 (0.121 g, 0.2 mmol) was stirred at ambient temperature for 5 hours in the presence of dimethyl sulphate (55 mg; 0.44 mmol) in 5 ml of 1,2-dichloroethane.
After reaction, the reaction mixture was concentrated. The residue obtained was washed with 5 ml of ethyl acetate. After the resulting precipitate had been isolated by filtration and dried, 113 mg of a fuchsia red powder corresponding to compound 19 were obtained.
The analyses were in accordance with the expected product.
The same methodology was applied to give compound 20. This was done using the following halo derivative:
2.5 g of a fuchsia red powder corresponding to compound 20 were obtained.
The same methodology was applied to give compound 21. This was done using the following halo derivative:
1.5 g of a fuchsia red powder corresponding to compound 21 were obtained.
2—Example of Dyeing Under Non-Oxidizing Conditions:
5×10−4 mol of compound 6, obtained above, were dissolved in 5 ml of a mixture of water (2.5 ml) and pH 10 buffer (2.5 ml) with the following composition:
2 g of ammonium acetate
40 ml of water
NH3 at 20% to a pH of 9-10
water to 100 ml.
100 g of the above composition were applied to hair at ambient temperature for 30 minutes. The hair was then rinsed with water and dried.
The hair was colored claret.
| Number | Date | Country | Kind |
|---|---|---|---|
| 04 53000 | Dec 2004 | FR | national |
This application claims benefit of U.S. Provisional Application No. 60/646,975, filed Jan. 27, 2005, the contents of which are incorporated herein by reference. This application also claims benefit of priority under 35 U.S.C. §119 to French Patent Application No. 04 53000, filed Dec. 15, 2004, the contents of which are also incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 60646975 | Jan 2005 | US |
