Dyeing compositions for keratinous fibres containing paraphenylenediamine derivatives with pyrrolidi

专利摘要:
The present invention relates to novel dyeing compositions for keratinous fibers containing one or more paraphenylenediamine derivatives having a pyrrolidinyl group as the oxidation base, and dyeing methods and dyeing kits using the compositions.
公开号:KR20010113945A
申请号:KR1020017014536
申请日:2001-03-13
公开日:2001-12-28
发明作者:비달로렁；떼라노바에릭；사벨르스떼판
申请人:조지안느 플로；로레알；
IPC主号:

专利说明:

DYEING COMPOSITIONS FOR KERATINOUS FIBRES CONTAINING PARAPHENYLENEDIAMINE DERIVATIVES WITH PYRROLIDINYL GROUP}, which contains a paraphenylenediamine derivative having a pyrrolidinyl group
[1] The present invention relates to a novel composition for the oxidative dyeing of keratin fibers, a dyeing method using the composition and a dyeing kit, containing as an oxidation base at least one para-phenylenediamine derivative having a pyrrolidinyl group.
[2] Keratin fibres, especially human hair, are oxidized dye precursors, commonly known as oxidizing bases, in particular heterocyclic bases such as ortho- or para-phenylenediamine, ortho- or para-aminophenol, or diaminopyrazole derivatives Dyeing with the containing dyeing composition is a known practice. Such oxidized dye precursors (oxidized bases) are colorless or off-white compounds and, when combined with oxidized products, can produce colored compounds and dyes by oxidative condensation methods.
[3] It is also known that the shade obtained with such an oxidizing base can be varied by combining the oxidizing base with a coupling agent or a color modifier, the color modifier being especially aromatic meta-diamine, meta-aminophenol, meta -Diphenol and certain heterocyclic compounds.
[4] Various molecules used as oxidation bases and coupling agents make it possible to obtain a wide range of colors.
[5] However, the so-called "permanent" coloring obtained using these oxidizing dyes must furthermore satisfy a certain number of requirements. Therefore, there should be no toxicological shortcomings, it is possible to obtain a desired color tone, and have a good persistence against external factors (light, climatic conditions, washing, permer waking, sweating or rubbing).
[6] The dye should also be able to hide gray hair and should be as nonselective as possible, which means that it is possible to avoid possible differences in color along the same keratin fibers, which may in fact be differently sensitized (ie damaged) between the terminal and hair roots. It should be the smallest possible.
[7] In the field of hair dyeing, para-phenylenediamine and para-toluylenediamine are widely used oxidation bases. These, together with the oxidative coupling agent, make it possible to obtain various shades.
[8] However, it is possible to give the hair a better toxicological profile than para-phenylenediamine or para-toluylenediamine, while at the same time giving the hair excellent properties of color intensity, various color tones, color uniformity and external factors. There is a need to find new oxidation bases (also known as colorants).
[9] Potential replacement for 2- (β-hydroxyethyl) -para-phenylenediamine or N, N-bis (β-hydroxyethyl) -para-phenylenediamine with para-phenylenediamine and para-toluylenediamine It is already proposed to use it, in particular in patent application GB 2 239 265. The same is true for 2- (hydroxyalkoxy) -para-phenylenediamine (see in particular US Pat. No. 5,538,516).
[10] However, N, N-bis- (β-hydroxyethyl) -para-phenylenediamine and 2- (β-hydroxyethyl) -para-phenylenediamine are present in the hair, para-phenylenediamine or para-tolu. It has the disadvantage of imparting a more limited range of hues than ylenediamine, and imparting a weaker color intensity and lower uniformity. The same applies to the case of 2- (hydroxyalkoxy) -para-phenylenediamine, which gives hairs a color that develops and changes over time.
[11] Furthermore, from the literature (see RL Bent et al., JACS 73, 3100, 1951), para-phenylenediamine in which one of the nitrogen atoms is included in a non-aromatic 6- or 7-membered carbon-based ring or heterocyclic ring The derivative is para-phenylenediamine in which one of the nitrogen atoms is replaced by two asymmetric substituents, which is not easier to oxidize than a para-phenylenediamine derivative in which one of the nitrogen atoms is substituted with two symmetric substituents. It is known that oxidation is not easier than derivatives.
[12] In the same paper it is also mentioned that para-phenylenediamine derivatives in which one of the nitrogen atoms is included in the non-aromatic 5-membered carbon-based ring are easier to oxidize than the respective derivatives mentioned above. Thus, N-pyrrolidine derivatives of para-phenylenediamine of this particular group, when compared with the above-mentioned para-phenylenediamine derivatives, are dynamically accelerated condensation with the coupling agent in basic and oxidative media. It is possible to obtain a reaction.
[13] However, oxidative bases that are too easy to oxidize and react with the coupling agent at an accelerated reaction rate generally lead to the formation of dyes on the outside of the keratinous fibers. Insufficient
[14] However, patent US 5 851 237 proposes the use of optionally substituted 1- (4-aminophenyl) pyrrolidine derivatives on the benzene nucleus to replace para-phenylenediamine. In this respect, the same patent very preferentially suggests the use of 1- (4-aminophenyl) pyrrolidine as a substitute for para-phenylenediamine.
[15] Currently, it is known in the literature that 1- (4-aminophenyl) pyrrolidine has a high allergic activity (R. L. Bent et al., J. A. C. S. 73, 3100, 1951).
[16] Patent US 5 993 491 also proposes the use of N- (4-aminophenyl) -2- (hydroxymethyl) pyrrolidine, optionally substituted on the benzene nucleus, to replace para-phenylenediamine. As a highly preferred compound claimed, the patent proposes N- (4-aminophenyl) -2- (hydroxymethyl) pyrrolidine optionally substituted with a methyl radical at position 3.
[17] However, it is clearly demonstrated that such compounds do not make it possible to impart coloration on the hair of a quality equivalent to that obtained with para-phenylenediamine due to the lack of strength and uniformity of the color obtained.
[18] Patent application JP 11 158 048 also proposes a hair-coloring composition which provides good spreadability, ease of application and resistance to shampoos. Such dye compositions are para-phenylenediamine derivatives optionally substituted with 1 to 4 substituents on the benzene nucleus and one of the nitrogen atoms is contained in a 5- to 7-membered carbon-based ring, or 1 to 4 on the benzene nucleus. Optionally substituted with four substituents, one of the nitrogen atoms being a radical Z ₁ and a radical Z ₂ (Z ₁ is an alkyl or aryl group or a heterocycle, Z ₂ is a Z ₃ is a hydrogen atom, an alkyl or aryl group or a heterocycle One or more compounds selected from para-phenylenediamine derivatives substituted with a radical-(CH ₂ -CH ₂ -O) -Z ₃ ).
[19] In view of the coloring power, ease of application, uniformity of the coloring obtained and in particular the sustaining power related to the action of the shampoo, the derivatives preferred in the Japanese patent application, namely N- (3-isopropyloxy-4-aminophenyl) -2 , 5-diethylpyrrolidine, N- (3-methyl-4-aminophenyl) -3- (2-hydroxyethyloxy) pyrrolidine and N- (3-methyl-4-aminophenyl) -2 It is shown that -methyl-4-hydroxypyrrolidine behaves like an oxidative base equivalent to the 4-aminoaniline derivative contained in the 6-membered piperidine ring functionalized by nitrogen atoms.
[20] However, when one of the nitrogen atoms of the para-phenylenediamine derivative is included in the 6-membered ring, the activation energy leading to the corresponding quinone-imine oxidation form is the most of the N, N-2 substituted para-phenylenediamine series. It is known to be one of the higher. These data show that the condensation reaction with the coupling agent is less efficient and imparts insufficient coloring properties to the hair in view of the strength and uniformity of the color obtained when compared with those obtained with para-phenylenediamine or para-toluylenediamine. It is concluded.
[21] The result of this is that the solution by para-phenylenediamine derivatives with nitrogen atoms contained in the functionalized pyrrolidine rings, proposed in patent application JP 11 158 048, is converted to para-phenylenediamine or para-toluylenediamine. It does not make it possible to give hair dyeing results equivalent to those obtained.
[22] Thus, having both good toxicological profile and properties, the compositions containing them have excellent properties for color strength, varying color tone, color uniformity (i.e. low selectivity) to the hair, and for various external attack factors that the hair may experience. It is clear that there is a real need to find new oxidation bases that make it possible to give lasting coloring.
[23] Applicants now fully surprisingly and unexpectedly find that certain phenylenediamine derivatives containing pyrrolidinyl groups of the formula (I), defined below, are not only suitable for use as oxidation bases for oxidative dyeing of keratin fibres, but also particularly powerful and relatively It has been found that this leads to non-selective coloring. They also make it possible to obtain dye compositions that impart coloration that is resistant to the various attack factors that the hair may experience.
[24] This finding forms the basis of the present invention.
[25] Accordingly, a first subject of the invention is a composition for the oxidative dyeing of keratin fibers, in particular human keratin fibers, such as hair, comprising a para-phenylenediamine derivative containing a pyrrolidinyl group of the formula (I) in a medium suitable for dyeing, And one or more oxidation bases selected from acid addition salts thereof:
[26] [Formula I]
[27]
[28] [In meals:
[29] R ₁ is a hydrogen atom; Halogen atoms selected from chlorine and bromine atoms; May comprise one or more double bonds and / or one or more triple bonds (the double bond may optionally be an aromatic group), and one or more carbon atoms may be replaced with oxygen, nitrogen or sulfur atoms or SO ₂ groups, Independently of each other, it represents a linear or branched C ₁ -C ₇ alkyl radical which may be substituted with one or more halogen atoms (branch (s) may form one or more 3- to 6-membered carbon-based rings); The radical R ₁ does not comprise a peroxide bond or a diazo, nitro or nitroso radical;
[30] R ₂ is a hydroxyl radical; Amino radicals; One or more hydroxyl or linear or branched C ₁ -C ₄ alkyl radicals wherein R ₃ is substituted with one or more radicals selected from the group consisting of halogen atoms, C ₁ -C ₂ alkoxy, amino or C ₁ -C ₂ aminoalkyl An -OR ₃ group representing a C ₃ -C ₄ alkyl radical substituted with a radical; R ₄ and R ₅ are, independently of one another, substituted with one or more radicals selected from the group consisting of a hydrogen atom, a halogen atom and a hydroxyl, C ₁ -C ₂ alkoxy, amino or C ₁ -C ₂ aminoalkyl radical Or a —NR ₄ R ₅ group representing a branched C ₁ -C ₄ alkyl radical.
[31] As mentioned above, the coloration obtained with the oxidizing dye composition according to the invention is strong, relatively non-selective, and also against the action of various external factors (light, bad weather, washing, perm waking, sweating and rubbing). Has good properties of resistance. Oxidative dye compositions according to the invention also make it possible to achieve a wide range of hues.
[32] According to the invention, it is indicated that one or more carbon atoms of the radical R ₁ may be replaced by an oxygen, nitrogen or sulfur atom or SO ₂ group, and / or said radical R ₁ comprises one or more double bonds and / or one or more triple bonds When doing this means, for example, that the following conversion can be performed;
[33]
[34] In particular, R ₁ is a hydrogen atom, linear or branched, saturated or unsaturated hydrocarbon-based chain, alkoxy, alkoxyalkyl, mono- or polyhydroxyalkyl, aminoalkyl, carboxyalkyl, hydroxyaminoalkyl and hydroxyalkoxy groups Can be selected. Among these substituents, R ₁ is in particular a hydrogen atom or methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, 2-hydroxy Ethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or 3-hydroxyethyloxy radicals. Among these substituents, R ₁ preferably represents a hydrogen atom or a methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy or 2-hydroxyethoxy radical.
[35] Among these substituents, R ₁ more preferably represents a hydrogen atom or a methyl radical.
[36] Among the substituents R ₂ useful in the present invention, R ₂ is a hydroxyl radical; Amino radicals; R ₃ is halogen atom, C ₁ -C ₂ alkoxy, amino and C ₁ -C ₂ -OR ₃ represents a linear or branched C ₁ -C ₄ alkyl radical substituted by one or more radicals selected from the group consisting of amino alkyl group; R ₄ and R ₅ are, independently of each other, substituted with one or more radicals selected from the group consisting of hydrogen atom, halogen atom and hydroxyl, C ₁ -C ₂ alkoxy, amino or C ₁ -C ₂ aminoalkyl radical Or a -NR ₄ R ₅ group representing a branched C ₁ -C ₄ alkyl radical. Preferably, R ₂ represents a hydroxyl, acetoxy, amino, methylamino, dimethylamino or 2-hydroxyethylamino radical. Among these substituents, R ₂ more preferentially represents a hydroxyl or amino radical.
[37] Among the para-phenylenediamine derivatives containing the pyrrolidinyl group of the formula (I), in particular, N- (4-aminophenyl) -3-hydroxypyrrolidine, N- (4-amino-2-methylphenyl) -3- Hydroxypyrrolidine, N- (4-amino-2-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-methoxyphenyl) -3-hydroxypyrrolidine, N -(4-amino-2- (2-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3-hydroxypy Lolidine, N- (4-amino-2- (1,2-dihydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methylphenyl) -3-hydroxypy Lolidine, N- (4-amino-3-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methoxyphenyl) -3-hydroxypyrrolidine, N- (4 -Amino-3- (2-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1,2-dihydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-aminofe ) -3-aminopyrrolidine, N- (4-amino-2-methylphenyl) -3-aminopyrrolidine, N- (4-amino-2-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-2-methoxyphenyl) -3-aminopyrrolidine, N- (4-amino-2- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4- Amino-2- (1-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-2- (1,2-dihydroxyethyl) phenyl) -3-hydroxypyrrolidine , N- (4-amino-3-methylphenyl) -3-aminopyrrolidine, N- (4-amino-3-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-3-meth Methoxyphenyl) -3-aminopyrrolidine, N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-3- (1-hydroxy Oxyethyl) phenyl) -3-aminopyrrolidine and N- (4-amino-3- (1,2-dihydroxyethyl) phenyl) -3-aminopyrrolidine, and acid addition salts thereof can do.
[38] Para-phenylenediamine derivatives comprising pyrrolidinyl groups of the formula (I), and methods for synthesizing them are known; See, in particular, patent application DE 4 241 532 (AGFA).
[39] The para-phenylenediamine derivative (s) and / or acid addition salt (s) thereof according to the invention comprising a pyrrolidinyl group of formula (I) are preferably from about 0.0005% by weight to the total weight of the dye composition 12% by weight and even more preferentially about 0.005% to 6% by weight.
[40] Suitable media (or supports) for dyeing generally consist of water or a mixture of water and one or more organic solvents to dissolve the compounds that are not sufficiently water-soluble. Organic solvents that may be mentioned include, for example, C ₁ -C ₄ lower alkanols such as ethanol and isopropanol; Glycerol; Glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and monomethyl ether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar Products and mixtures thereof.
[41] The solvent may preferably be present in a proportion of about 1% to 40% by weight, and more preferably about 5% to 30% by weight relative to the total weight of the dye composition.
[42] The pH of the dye composition according to the invention is generally about 3-12, preferably about 5-11. This can be adjusted to the desired value using an acidifying or basicizing agent generally used for dyeing keratin fibers, or alternatively using conventional buffer systems.
[43] Acidifying agents that may be mentioned are, for example, mineral acids or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acid.
[44] According to certain embodiments, the basicizing agent is selected from alkanolamines, diaminoalkanes and aqueous ammonia.
[45] For the purposes of the present invention, the term "alkanolamine" is any saturated or unsaturated, linear or branched hydrocarbon-based compound, containing 2 to 100 carbon atoms, and (i) preferably C ₁ -C ₄ alkyl, for example, a mono- or polyhydroxy alkyl and substituted C ₁ -C ₄ alkyl, one or two substituents optionally substituted with one or more functional groups such as amine and (ii) one or more amine functional groups that are not included in the It contains hydroxyl functional groups. Preferably, the hydrocarbon-based chain is saturated.
[46] Among the alkanolamines that can be used according to the invention, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3 Propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-butanol, tris (hydroxymethyl) aminomethane, 2-aminoethylethanolamine, 1-diethylamino-2 Mention may be made of, 3-propanediol, 2-dimethylamino-2-methyl-1-propanol, dimethylethanolamine, diethylethanolamine, ethyl monoethanolamine and methylethanolamine. Preferably, monoethanolamine is used.
[47] The diaminoalkanes used according to the invention are preferably diaminoalkanes of formula II:
[48] [Formula II]
[49]
[50] [Wherein W is an alkylene moiety optionally substituted with a hydroxyl group or a C ₁ -C ₄ alkyl radical; R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and represent a hydrogen atom, a C ₁ -C ₄ alkyl radical or a C ₁ -C ₄ hydroxyalkyl radical. Preferably, W is a propylene moiety. Even more preferentially, the diaminoalkane is diaminopropane.
[51] Of all the alkalizing agents which can be used according to the invention, aqueous ammonia is preferably used.
[52] The alkalizing agent (s) is from about 0.1% to about 20% by weight of the ready-to-use oxidation dye composition or the composition for oxidative dyeing according to the present invention, relative to the total weight of the composition for oxidative dyeing or the instant oxidizing dye composition. It is present at a concentration of from about 0.5% by weight to about 10% by weight.
[53] According to one preferred embodiment, the oxidizing dye composition according to the invention also contains one or more coupling agents to modify the hue obtained by using the compound of the formula (I) or to enrich the hue with gloss.
[54] Coupling agents which can be used in the oxidative dye composition according to the invention can be selected from among those commonly used for oxidative dyeing, among which meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthol And heterocyclic coupling agents such as pyrazolo [1,5-b] -1,2,4-triazole, pyrazolo [3,2-c] -1,2,4-triazole, pyrazole-5 Mention may be made of -one, pyridine, indole, indolin, indazole, benzimidazole, benzothiazole, benzoxazole, 1,3-benzodioxol and quinoline.
[55] According to certain embodiments, the coupling agent (s) are heterocyclic coupling agents, substituted meta-diphenols, substituted meta-phenylenediamines, naphthols and acylated naphthols, and meta-aminophenols of Formula III, and Their acid addition salts are selected from:
[56] [Formula III]
[57]
[58] [In meals:
[59] R ₅ represents a hydrogen atom or a C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl radical,
[60] R ₆ represents a hydrogen atom, a C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy radical or a halogen atom selected from chlorine, bromine and fluorine,
[61] R ₇ is a hydrogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, C ₁ -C ₄ monohydroxy Alkoxy or a C ₂ -C ₄ polyhydroxyalkoxy radical.
[62] Among the substituted meta-diphenols that can be used as coupling agents in the dye compositions according to the invention, the compounds preferably to be used are compounds of the formula (VI), and acid addition salts thereof:
[63] [Formula VI]
[64]
[65] [In meals:
[66] R ₈ and R ₉ may be the same or different and represent a hydrogen atom, a C ₁ -C ₄ alkyl radical, or a halogen atom selected from chlorine, bromine and fluorine, at least one of the radicals R ₈ and R ₉ represents a hydrogen atom Other than that.
[67] More specifically mentioned among the substituted meta-diphenols of the above formula VI are 2-methyl-1,3-dihydroxybenzene, 4-chloro-1,3-dihydroxybenzene and 2-chloro-1, 3-dihydroxybenzenes, and their acid addition salts.
[68] Among the substituted meta-phenylenediamines that can be used as coupling agents in the dye compositions according to the invention, the compounds to be used preferably are compounds of the formula (V), and acid addition salts thereof:
[69]
[70] [In meals:
[71] R ₁₀ represents a hydrogen atom or a C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl radical;
[72] R ₁₁ and R ₁₂ may be the same or different and represent a hydrogen atom or a C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkoxy or C ₂ -C ₄ polyhydroxyalkoxy radical;
[73] R ₁₃ represents a hydrogen atom, C ₁ -C ₄ alkoxy, C ₁ -C ₄ aminoalkoxy, C ₁ -C ₄ monohydroxyalkoxy or C ₂ -C ₄ polyhydroxyalkoxy radical or 2,4-diaminophenoxy Represents a cyalkoxy radical; It is understood that at least one of the radicals R ₁₀ to R ₁₃ is other than a hydrogen atom.
[74] More specifically mentioned among the substituted meta-phenylenediamines of the above formula (V) are 3,5-diamino-1-ethyl-2-methoxybenzene, 3,5-diamino-2-methoxy-1- Methylbenzene, 2,4-diamino-1-ethoxybenzene, 1,3-bis (2,4-diaminophenoxy) propane, bis (2,4-diaminophenoxy) methane, 1- (β -Aminoethyloxy) -2,4-diaminobenzene, 2-amino-1- (β-hydroxyethyloxy) -4-methylaminobenzene, 2,4-diamino-1-ethoxy-5-methyl Benzene, 2,4-diamino-5- (β-hydroxyethyloxy) -1-methylbenzene, 2,4-diamino-1- (β, γ-dihydroxypropyloxy) benzene, 2,4 -Diamino-1- (β-hydroxyethyloxy) benzene and 2-amino-4-N- (β-hydroxyethyl) amino-1-methoxybenzene, and acid addition salts thereof.
[75] Among the heterocyclic coupling agents which can be used in the dye composition according to the present invention, mention may be made particularly of indole derivatives, indolin derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyrazoloazole derivatives, Roloazole derivatives, imidazoloazole derivatives, pyrazolopyrimidine derivatives, pyrazoline-3,5-dione derivatives, pyrrolo [3,2-d] oxazole derivatives, pyrazolo [3,4-d] thiazole Derivatives, thiazoloazole S-oxide derivatives and thiazoloazole S, S-dioxide derivatives, and acid addition salts thereof.
[76] Among the indole derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, mention may be made in particular of the compounds of the formula (VI), and acid addition salts thereof:
[77] [Formula VI]
[78]
[79] [In meals:
[80] R ₁₄ is a hydrogen atom, C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, or an amine mono- or di-substituted with a C ₁ -C ₄ alkyl group A C ₁ -C ₄ aminoalkyl radical;
[81] R ₁₅ represents a hydrogen atom or a C ₁ -C ₄ alkyl radical;
[82] R ₁₆ represents a hydrogen atom or a C ₁ -C ₄ alkyl or hydroxyl radical;
[83] -X represents a hydroxyl radical, or a radical NHR _{17 wherein} R ₁₇ represents a hydrogen atom or a C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl radical.
[84] More particularly mentioned among the indole derivatives of the above formula (V) are 4-hydroxyindole, 6-hydroxyindole, 7-aminoindole, 6-aminoindole, 7-hydroxyindole, 7-ethyl-6- (β -Hydroxyethyl) aminoindole, 4-aminoindole, 6-hydroxy-1-methylindole, 5,6-dihydroxyindole, 4-hydroxy-1-N-methylindole, 4-hydroxy-2 -Methylindole, 4-hydroxy-5-methylindole, 4-hydroxy-1-N- (β-hydroxyethyl) indole, 4-hydroxy-1-N- (β-hydroxypropyl) indole, 1-N- (β-dihydroxypropyl) -4-hydroxyindole, 4-hydroxy-1-N- (β-hydroxyethyl) -5-methylindole and 1-N- (γ-dimethylamino Propyl) -4-hydroxyindole, and their acid addition salts.
[85] Among the indolin derivatives which may be used as heterocyclic coupling agents in the dye compositions according to the invention, mention may be made in particular of 4-hydroxyindolin, 6-hydroxyindolin, 6-aminoindolin and 5,6 -Dihydroxyindolin, and acid addition salts thereof.
[86] Among the benzimidazole derivatives that can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mention may be made of the compounds of the formula (VII) and their acid addition salts:
[87] [Formula VII]
[88]
[89] [In meals:
[90] R ₁₈ represents a hydrogen atom or a C ₁ -C ₄ alkyl radical,
[91] R ₁₉ represents a hydrogen atom or a C ₁ -C ₄ alkyl or phenyl radical,
[92] R ₂₀ represents a hydroxyl, amino or methoxy radical,
[93] R ₂₁ represents a hydrogen atom or a hydroxyl, methoxy or C ₁ -C ₄ alkyl radical, provided that
[94] When R ₂₀ represents an amino radical, occupies 4 positions,
[95] When R ₂₀ occupies four positions, R ₂₁ occupies seven positions,
[96] When R ₂₀ occupies 5 positions, R ₂₁ occupies 6 positions].
[97] Among the benzimidazole derivatives of the above formula (VII), more particularly mentionable may be 4-hydroxybenzimidazole, 4-aminobenzimidazole, 4-hydroxy-7-methylbenzimidazole, 4-hydroxy-2 -Methylbenzimidazole, 1-butyl-4-hydroxybenzimidazole, 4-amino-2-methylbenzimidazole, 5,6-dihydroxybenzimidazole, 5-hydroxy-6-methoxybenz Imidazole, 4,7-dihydroxybenzimidazole, 4,7-dihydroxy-1-methylbenzimidazole, 4,7-dimethoxybenzimidazole, 5,6-dihydroxy-1-methyl Benzimidazole, 5,6-dihydroxy-2-methylbenzimidazole and 5,6-dimethoxybenzimidazole, and acid addition salts thereof.
[98] Among the benzomorpholine derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mention may be made of the compounds of the formula VIII and their acid addition salts:
[99] [Formula VIII]
[100]
[101] [In meals:
[102] R ₂₂ and R ₂₃ may be the same or different and represent a hydrogen atom or a C ₁ -C ₄ alkyl radical,
[103] Z represents a hydroxyl or amino radical.
[104] More specifically mentioned among the benzomorpholine derivatives of the above formula (VIII) are 6-hydroxy-1,4-benzomorpholine, N-methyl-6-hydroxy-1,4-benzomorpholine and 6-amino- 1,4-benzomorpholine, and acid addition salts thereof.
[105] Among the sesamol derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, mention may be made in particular of compounds of the general formula (IX) and acid addition salts thereof:
[106] [Formula IX]
[107]
[108] [In meals:
[109] R ₂₄ represents a hydroxyl, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ monohydroxyalkylamino or C ₂ -C ₄ polyhydroxyalkylamino radical,
[110] R ₂₅ represents hydrogen or a halogen atom or a C ₁ -C ₄ alkoxy radical.
[111] More specifically mentioned among the sesamol derivatives of the formula (IX) are 2-bromo-4,5-methylenedioxyphenol, 2-methoxy-4,5-methylenedioxyaniline and 2- (β-hydroxy Ethyl) amino-4,5-methylenedioxybenzene, and their acid addition salts.
[112] Among the pyrazoloazole derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the following patents and patent applications: FR-A-2 075 583, EP-A-0 119 860, EP-A-0 285 274, EP-A-0 244 160, EP-A-0 578 248, GB 1 458 377, US 3 227 554, US 3 419 391, US 3 061 432, US 4 500 630 , US 3 725 067, US 3 926 631, US 5 457 210, JP 84/99437, JP 83/42045, JP 84/162548, JP 84/171956, JP 85/33552, JP 85/43659, JP 85/172982 , Compounds described in JP 85/190779 and the following publications: Chem. Ber. 32, 797 (1899), Chem. Ber. 89, 2550, (1956), J. Chem. Soc. Perkin trans l, 2047, (1977), J. Prakt. Chem., 320, 533, (1978); The above teachings form an important part of this patent application.
[113] Most particularly mentionable pyrazoloazole derivatives are:
[114] 2-methylpyrazolo [1,5-b] -1,2,4-triazole,
[115] 2-ethylpyrazolo [1,5-b] -1,2,4-triazole,
[116] 2-isopropylpyrazolo [1,5-b] -1,2,4-triazole,
[117] 2-phenylpyrazolo [1,5-b] -1,2,4-triazole,
[118] 2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole,
[119] 7-chloro-2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole,
[120] 3,6-dimethylpyrazolo [3,2-c] -1,2,4-triazole,
[121] 6-phenyl-3-methylthiopyrazolo [3,2-c] -1,2,4-triazole,
[122] 6-aminopyrazolo [1,5-a] benzimidazole,
[123] And acid addition salts thereof.
[124] Among the pyrroloazole derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the following patent applications and patents: US 5 256 526, EP-A-0 557 851, EP -A-0 578 248, EP-A-0 518 238, EP-A-0 456 226, EP-A-0 488 909, EP-A-0 488 248, and the following publications:
[125] -D.R. Liljegren Ber. 1964, 3436;
[126] -E.J. Browne, J. C. S., 1962, 5149;
[127] P. Magnus, J. A. C. S., 1990, 112, 2465;
[128] P. Magnus, J. A. C. S., 1987, 109, 2711;
[129] -Angew. Chem. 1960, 72, 956; And
[130] -Rec. Trav. Chim. The compounds described in 1961, 80, 1075; The above teachings form an important part of this patent application.
[131] Most particularly mentionable pyrroloazole derivatives are:
[132] 5-cyano-4-ethoxycarbonyl-8-methylpyrrolo [1,2-b] -1,2,4-triazole,
[133] 5-cyano-8-methyl-4-phenylpyrrolo [1,2-b] -1,2,4-triazole,
[134] 7-amido-6-ethoxycarbonylpyrrolo [1,2-a] benzimidazole,
[135] And acid addition salts thereof.
[136] Among the imidazoloazole derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the following patent applications and patents: US 5 441 863; JP 62-279 337; The compounds described in JP 06-236 011 and JP 07-092 632, the teachings of which form an important part of this patent application.
[137] More particularly mentionable imidazoloazole derivatives are:
[138] 7,8-dicyanoimidazolo [3,2-a] imidazole,
[139] 7,8-dicyano-4-methylimidazolo [3,2-a] imidazole,
[140] And acid addition salts thereof.
[141] Among the pyrazolopyrimidine derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the compounds described in the following patent application: EP-A-0 304 001, The teachings form an important part of this patent application.
[142] Most particularly mentionable pyrazolopyrimidine derivatives are:
[143] Pyrazolo [1,5-a] pyrimidin-7-one,
[144] 2,5-dimethylpyrazolo [1,5-a] pyrimidin-7-one,
[145] 2-methyl-6-ethoxycarbonylpyrazolo [1,5-a] pyrimidin-7-one
[146] 2-methyl-5-methoxymethylpyrazolo [1,5-a] pyrimidin-7-one,
[147] 2-tert-butyl-5-trifluoromethylpyrazolo [1,5-a] pyrimidin-7-one,
[148] 2,7-dimethylpyrazolo [1,5-a] pyrimidin-5-one,
[149] And acid addition salts thereof.
[150] Among the pyrazoline-3,5-dione derivatives that can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the following patent applications and patents: JP 07-036159, JP 07-084348 And compounds described in US 4 128 425, and the following publications:
[151] L. WYZGOWSKA, Acta. Pol. Pharm. 1982, 39 (1-3), 83.
[152] E. HANNIG, Pharmazie, 1980, 35 (4), 231
[153] -M.H. ELNAGDI, Bull. Chem. Soc. Jap., 46 (6), 1830, 1973
[154] -G. CARDILLO, Gazz. Chim. Ital. 1966, 96, (8-9), 973, and
[155] The above teachings form an important part of this patent application.
[156] Most particularly mentionable pyrazoline-3,5-dione derivatives are:
[157] 1,2-diphenylpyrazoline-3,5-dione,
[158] 1,2-diethylpyrazoline-3,5-dione,
[159] And acid addition salts thereof.
[160] Among the pyrrolo [3,2-d] oxazole derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the compounds described in patent application JP 07 325 375, The teachings of this form an important part of this patent application.
[161] Among the pyrazolo [3,4-d] thiazole derivatives that can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the patent applications JP 07 244 361 and [J. Heterocycl. Chem. 16 , 13, (1979).
[162] Among the thiazoloazole S-oxides and thiazoloazole S, S-dioxide derivatives which can be used as heterocyclic coupling agents in the dye compositions according to the invention, more particularly mentionable are the compounds described in the literature :
[163] JP 07 098 489;
[164] -Khim. Geterotsilk. Soedin, 1967, p. 93;
[165] J. Prakt. Chem., 318 , 1976, p. 12;
[166] -Indian J. Heterocycl. Chem. 1995, 5 (2), p. 135;
[167] -Acta. Pol. Pharm. 1995, 52 (5), 415;
[168] Heterocycl. Commun. 1995, 1 (4), 297;
[169] Arch. Pharm. (Weinheim, Ger.), 1994, 327 (12), 825.
[170] Among the naphthols and acylated naphthols which may be used as coupling agents in the dye compositions according to the invention, the compounds to be preferably used are the compounds of the formula (X) and acid addition salts thereof:
[171] [Formula X]
[172]
[173] [In meals:
[174] R ₂₆ represents a hydrogen atom or a —CO—R group in which R represents a C ₁ -C ₄ alkyl radical;
[175] R ₂₇ represents a hydrogen atom, a hydroxyl or C ₁ -C ₄ alkyl radical, or a —SO ₃ H group;
[176] R ₂₈ represents a hydrogen atom or a hydroxyl radical; It is understood that at least one of the radicals R ₂₆ to R ₂₈ is other than a hydrogen atom.
[177] Among the naphthols and acylated naphthols of formula X which can be used as coupling agents in the dye compositions according to the invention, mention may be made especially of 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,5 Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1-acetoxy-2-methyl-naphthalene, 1-hydroxy-2-methylnaphthalene and 1-hydroxy-4-naphthalenesulfonic acid, and acids thereof Addition salts.
[178] When present, the coupling agent (s) preferably represent approximately 0.0001% to 10%, more preferably 0.005% to 5% by weight relative to the total weight of the dye composition.
[179] The dye compositions according to the invention may further contain one or more further oxidation bases, which may further be chosen from the oxidation bases commonly used in oxidative dyeing, of which particular mention may be made according to the invention. Para-phenylenediamines, bis (phenyl) alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases other than the compounds of formula (I), and acid addition salts thereof.
[180] According to certain embodiments, additional bases are selected from heterocyclic oxidation bases, double bases, substituted para-aminophenols, ortho-aminophenols, para-phenylenediamine derivatives of formula II below, and acid addition salts thereof Is selected:
[181] [Formula II]
[182]
[183] [In meals:
[184] -R ₅ is a hydrogen atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) an alkyl radical, a C ₁ -C ₄ alkyl radical substituted with one or more nitrogenous groups, a phenyl radical or a 4′-aminophenyl radical;
[185] R ₆ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) an alkyl radical or a C ₁ -C ₄ alkyl radical substituted with one or more nitrogenous groups;
[186] R ₇ is a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₁ -C ₄ hydroxyalkoxy radical, acetyl Amino (C ₁ -C ₄ ) alkoxy radicals, C ₁ -C ₄ mesylaminoalkoxy radicals or carbamoylamino (C ₁ -C ₄ ) alkoxy radicals,
[187] R ₈ represents hydrogen or a halogen atom or a C ₁ -C ₄ alkyl radical.
[188] Among the para-phenylenediamines of the formula (II) which can be used as further oxidation bases in the dye compositions according to the invention, more particularly mentionable are 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-amino-N, N-bis (β-hydroxyethyl) -2-methylaniline, 4-amino-2-chloro-N, N-bis (β-hydroxyethyl) aniline, 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-pe Rendiamine, N, N- (ethyl-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 and N- (β-methoxyethyl) -para-phenylenediamine, and acid addition salts thereof.
[189] Among the para-phenylenediamines represented by the above formula (II), 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) Most particularly preferred are -para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine and acid addition salts thereof.
[190] Even more preferentially, 2-β-hydroxyethyl-para-phenylenediamine, N, N-bis (β-hydroxyethyl) -para-phenylenediamine, and acid addition salts thereof are selected from Formula II above. Preferred among para-phenylenediamine.
[191] According to the invention, the term "double base" is understood to denote a compound comprising at least two aromatic rings with amino and / or hydroxyl groups.
[192] Among the dual bases which can be used as further oxidation bases in the dye compositions according to the invention, of particular mention are the double bases corresponding to the general formula (III) and acid addition salts thereof:
[193] [Formula III]
[194]
[195] [In meals:
[196] Z ₁ and Z ₂ represent the hydroxyl or —NH ₂ radicals which may be the same or different and which may be substituted with a C ₁ -C ₄ alkyl radical or linker arm Y;
[197] The linking arm Y may be interrupted or terminated with one or more nitrogenous groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and optionally substituted with one or more hydroxyl or C ₁ -C ₆ alkoxy radicals , Linear or branched alkylene chains containing 1 to 14 carbon atoms;
[198] R ₉ and R ₁₀ are hydrogen or halogen atoms, C ₁ -C ₄ alkyl radicals, C ₁ -C ₄ monohydroxyalkyl radicals, C ₂ -C ₄ polyhydroxyalkyl radicals, C ₁ -C ₄ aminoalkyl radicals Or the linking arm Y;
[199] R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and represent a hydrogen atom, a linking arm Y or a C ₁ -C ₄ alkyl radical;
[200] It is understood that the double base of Formula III contains only one linking arm Y per molecule].
[201] Among the nitrogenous groups present in the double base of the above formula (III), mention may be made especially of amino, mono (C ₁ -C ₄ ) alkylamino, di (C ₁ -C ₄ ) alkylamino, tri (C ₁ -C ₄ ) alkylamino, monohydroxy (C ₁ -C ₄ ) alkylamino, imidazolinium and ammonium radicals.
[202] Among the double bases of the general formula (III), more particularly mentionable are 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-aminophenyl) tetramethylenediamine, N, N '-Bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (Ethyl) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane, and these Acid addition salt.
[203] Among these double bases of formula III, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, 1,8-bis ( Particular preference is given to 2,5-diaminophenoxy) -3,5-dioxaoctane, or one of their acid addition salts.
[204] Among the substituted para-aminophenols that can be used as the second oxidation base in the dye compositions according to the invention, of particular mention are the substituted para-aminophenols of the formula IV and their acid addition salts:
[205] [Formula IV]
[206]
[207] [In meals:
[208] R ₁₇ is hydrogen or a halogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl, C ₁ -C ₄ amino Alkyl or hydroxy (C ₁ -C ₄ ) alkylamino (C ₁ -C ₄ ) alkyl radicals,
[209] R ₁₈ is hydrogen or a halogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, C ₁ -C ₄ aminoalkyl, C ₁ -C ₄ A cyanoalkyl or a (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl radical,
[210] It is understood that at least one of the radicals R ₁₇ or R ₁₈ is other than a hydrogen atom.
[211] Among the para-aminophenols of the above formula IV, more particularly mentionable may be para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 4-amino-3-hydroxy Methylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethylaminomethyl) phenol, 4-amino-2-fluorophenol, and acid addition salts thereof.
[212] Among the ortho-aminophenols which may be used as further oxidation bases in the dye compositions according to the invention, more particularly mentionable are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol And 5-acetamido-2-aminophenol, and acid addition salts thereof.
[213] Among the heterocyclic bases that can be used as the oxidation base in the dye compositions according to the invention, more particularly mentionable are pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and acid addition salts thereof.
[214] Among the pyridine derivatives, more particularly mentioned may be mentioned, for example, the compounds described in patents GB 1 026 978 and GB 1 153 196, such 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 their Acid addition salts.
[215] Among the pyrimidine derivatives, more particular mention may be made, for example, of German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 05 163 124; Compounds described in European Patent 0 770 375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy Hydroxy-4,5,6-triaminopyrimidine, 6-hydroxy-2,4,5-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5, 6-triaminopyrimidine and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048, among which
[216] Pyrazolo [1,5-a] pyrimidine-3,7-diamine;
[217] 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
[218] Pyrazolo [1,5-a] pyrimidine-3,5-diamine;
[219] 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
[220] 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
[221] 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
[222] 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
[223] 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol, 2-[(3-aminopyrazolo [1,5-a] pyrimidin-7-yl)-( 2-hydroxyethyl) amino] ethanol, 2-[(7-aminopyrazole [1,5-a] pyrimidin-3-yl)-(2-hydroxyethyl) amino] ethanol, 5,6-dimethyl Pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5, N7, N7-tetra Methylpyrazolo [1,5-a- [yrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo [1,5-a] pyrimidine, acid thereof When addition salts and tautomeric equilibrium are present, mention may be made of their tautomeric forms.
[224] Among the pyrazole derivatives, more particularly mentionable are described in patent DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988. Compounds such as 4,5-diamino-1-methyl-pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-dia Mino-1,3-dimethylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 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 acid addition salts thereof.
[225] If used, the further oxidation base (s) preferably represent from about 0.0005% to 12% by weight, and more preferably from about 0.005% to 6% by weight relative to the total weight of the dye composition.
[226] In general, acid addition salts which can be used in the contents of the dye compositions of the invention (compounds of formula I, coupling agents and further oxidation bases) are in particular hydrochloride, hydrobromide, sulphate, citrate, succinate, tartrate , Lactate, phosphate and acetate.
[227] The dye compositions according to the invention may also contain one or more direct dyes. Such direct dyes may be synthetic direct dyes and / or natural dyes selected from azo dyes, quinone dyes, triarylmethane dyes, indoamine dyes and azine dyes. Synthetic direct dyes that can be used according to the invention can be nonionic, anionic or cationic.
[228] Among the synthetic azo direct dyes that can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954, the contents of which form an important part of the invention. have.
[229] Among the azo direct dyes, mention may be made of 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, Disperse Black 9. Among these, 1- (4'-aminodiphenylazo) -2 Mention may be made of -methyl-4-bis (β-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid.
[230] Among the synthetic quinone direct dyes, mention may be made of: 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 compounds:
[231] 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone,
[232] 1-aminopropylamino-4-methylaminoanthraquinone,
[233] 1-aminopropylaminoanthraquinone,
[234] 5-β-hydroxyethyl-1,4-diaminoanthraquinone,
[235] 2-aminomethylaminoanthraquinone,
[236] 1,4-bis (β, γ-dihydroxypropylamino) anthraquinone.
[237] Among the synthetic azine direct dyes, mention may be made of: Basic Blue 17, BasicRed 2.
[238] Among the synthetic triarylmethane direct dyes that can be used according to the invention, mention may be made of: Basic Green 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic Blue 7, Acid Violet 49, Basic Blue 26, Acid Blue 7.
[239] Among the synthetic indoamine direct dyes that may be used according to the invention, mention may be made of:
[240] 2-β-hydroxyethylamino-5- [bis (β-4′-hydroxyethyl) amino] anilino-1,4-benzoquinone
[241] 2-β-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone
[242] 3-N- (2'-chloro-4'-hydroxy) phenylacetylamino-6-methoxy-1,4-benzoquinoneimine
[243] 3-N- (3'-chloro-4'-methylamino) phenylureido-6-methyl-1,4-benzoquinoneimine
[244] 3- [4'-N- (ethylcarbamylmethyl) amino] phenylureido-6-methyl-1,4-benzoquinoneimine.
[245] For the purposes of the present invention, the term "natural dye" means a compound present in nature, which is obtained by extraction or chemically reproduced. Among the natural direct dyes that can be used according to the invention, there are lawsonone, juglone, alizarin, purpurine, carminic acid, kermesic acid, Mention may be made of purpurogallin, protocatechaldehyde, indigo, isatitin, curcumin, spinulosin and apigenidin. . Extracts or baths containing such natural dyes, in particular henna-based poultices or extracts, may also be used.
[246] Synthetic direct dye (s) and / or natural dye (s) according to the invention represent approximately 0.001% to 20% by weight, and more preferably approximately 0.005% to 10% by weight relative to the total weight of the composition.
[247] The dye compositions according to the invention are also useful for various auxiliaries commonly used in compositions for dyeing 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, antioxidants, penetrants, sequestrants, perfumes, buffers, dispersants, conditioners such as, for example, volatile or nonvolatile silicones, modified or non- It may contain modified silicones, film-forming agents, ceramides, preservatives and opacifying agents.
[248] According to certain embodiments, the dye compositions of the invention contain one or more polymers selected from:
[249] (i) amphoteric polymers,
[250] (ii) a cationic polymer comprising repeat units of formula (II) or (III), and
[251] (iii) a polymer other than above, which is amphiphilic and comprises at least one hydrocarbon chain,
[252] Structural Formula (II):
[253]
[254] [In meals:
[255] R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and represent an aliphatic, cycloaliphatic or arylaliphatic radical or lower hydroxyalkylaliphatic radical comprising 1 to 20 carbon atoms, or alternatively , R ₅ , R ₆ , R ₇ and R ₈ together or separately, together with the nitrogen atom to which they are attached, constitute a heterocycle optionally containing a second hetero atom other than nitrogen, or alternatively, R ₅ , R ₆ , R ₇ and R ₈ are nitrile, ester, acyl, amide or substituted with a -CO-OR ₁₃ -D or -CO-NH-R ₁₃ -D group wherein R ₁₃ is alkylene and D is a quaternary ammonium group Linear or branched C ₁ -C ₆ alkyl radicals;
[256] A ₁ and B ₁ may be linear or branched, saturated or unsaturated, and at least one aromatic ring connected or inserted into the main chain, or at least one oxygen or sulfur atom, or sulfoxide, sulfone, disulfide, amino, alkylamino A polymethylene group containing 2 to 20 carbon atoms which may contain hydroxyl, quaternary ammonium, ureido, amide or ester groups;
[257] A ₁ , R ₅ and R ₇ together with the two nitrogen atoms to which they are attached may form a piperazine ring; Furthermore, if A ₁ represents a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, then B ₁ also represents-(CH wherein n is 1 to 100, preferably 1 to 50 and T represents ₂ ) _n- CO-T-OC- (CH ₂ ) _n -groups can be represented:
[258] a) a glycol moiety of the formula: -O-Z-O-, wherein Z represents a linear or branched hydrocarbon-based radical or a group corresponding to one or more of the following formulas:
[259] -(CH ₂ -CH ₂ -O) _x -CH ₂ -CH _2-
[260] -[CH ₂ -CH (CH ₃ ) -O] _y -CH ₂ -CH (CH ₃ )-
[261] (Wherein x and y represent an integer from 1 to 4 representing a limited and unique degree of polymerization, or any number from 1 to 4 representing an average degree of polymerization);
[262] b) bis-secondary diamine residues such as piperazine derivatives;
[263] c) Y is a linear or branched hydrocarbon-based radical, or alternatively a divalent radical:
[264] -CH ₂ -CH ₂ -SS-CH ₂ -CH _2-
[265] A bis-primary diamine residue of the formula -NH-Y-NH-;
[266] d) ureylene groups of the formula -NH-CO-NH-;
[267] X ₁ ⁻ is an anion derived from mineral or organic acids and preferably chlorine or bromine];
[268] Structural formula (III)
[269]
[270] [In meals:
[271] R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and represent a hydrogen atom or methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) represents a _p OH radical (wherein p is equal to 0 or an integer from 1 to 6),
[272] Provided that R ₉ , R ₁₀ , R ₁₁ and R ₁₂ do not represent a hydrogen atom at the same time,
[273] R and s, which may be the same or different, are an integer from 1 to 6,
[274] D is 0 or represents a-(CH ₂ ) _q -CO- group (q is equal to 0 or an integer from 1 to 34),
[275] A represents a dihalide radical, or preferably, -CH ₂ -CH ₂ -O-CH ₂ -CH _2- ,
[276] X ₂ ⁻ represents an anion derived from a mineral or organic acid, preferably a halogen atom.
[277] Cationic polymers having repeating units of formula (II) preferably have a number-average molecular weight of generally from 1 000 to 100 000.
[278] Polymers of this type are in particular French patents 2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 and patent US 2 273 780, 2 375 853, 2 388 614, 2 454 547, 3 206 462, 2 261 002, 2 271 378, 3 874 870, 4 001 432, 3 929 990, 3 966 904, 4 005 193, 4 025 617, 4 025 627, 4 025 653, 4 026 945 and 4 027 020 have.
[279] According to the invention, among these cationic polymers having repeating units of formula (II), more particularly used are those consisting of repeating units corresponding to the following formula (IV).
[280]
[281] [Wherein, R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be the same or different and represent an alkyl or hydroxyalkyl radical comprising approximately 1 to 4 carbon atoms, and n and p are approximately 2 to An integer ranging from 20 and X ₃ ⁻ is an anion derived from a mineral acid or an organic acid.
[282] More particularly, R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ represent methyl radicals, n and p are each equal to 6 and 3, and X ₃ ⁻ has units of the formula (IV) such as Cl ⁻ Preference is also given to using polymers; This polymer has the INCI name: Hexadimethrine Chloride.
[283] Cationic polymers having repeating units of formula (III) are described in particular in the patent application EP-A-122 324 and in the methods described in US Pat. Nos. 4,157, 388, 4, 390 689, 4, 702 906 and 4, 719, 282. Can be prepared accordingly.
[284] Among these polymers it is more particularly preferred according to the invention to use those having a molecular weight of less than 100 000, consisting of repeating units corresponding to the following structural formula (V), preferably measured by carbon-13 NMR:
[285] -(-N ⁺ (CH ₃ ) _2- (CH ₂ ) _r -NH-CO-D-NH- (CH ₂ ) _r -N ⁺ (CH ₃ ) _2- (CH ₂ ) ₂ -O- (CH _{2) ^{) 2 -] - 2X - (}} V)
[286] [Where r represents an integer ranging from approximately 1 to 6, and D can represent a 0 or-(CH ₂ ) _q -CO- group, where q represents a number such as 4 or 7. And X ⁻ is an anion derived from mineral or organic acid.
[287] More particularly preferred among the cationic polymers of formula (V) are:
[288] a) D represents a-(CH ₂ ) ₄ -CO- group, X represents a chlorine atom and the molecular weight measured by carbon-13 NMR (C ¹³ NMR) is about 5 600; This type of polymer is proposed by the company Miranol under the name Mirapol-AD1,
[289] b) D represents a-(CH ₂ ) ₇ -CO- group, X represents a chlorine atom and the molecular weight measured by carbon-13 NMR (C ¹³ NMR) is about 8100; Polymers of this type are proposed by the company Miranol under the name Mirapol-AZ1,
[290] c) D has a value of 0, X has a chlorine atom and a molecular weight of about 25 500 as measured by carbon-13 NMR (C ¹³ NMR); This type of polymer is sold by Miranol under the name Mirapol-A15,
[291] d) "block copolymers" formed from units corresponding to the polymers described in paragraphs a) to c), the name Mirapol-9 (C ¹³ NMR molecular weight about 7 800), Mirapol-175 (C ¹³ NMR molecular weight approx. 8 000) and Mirapol-95 (C ¹³ NMR molecular weight about 12 500).
[292] Even more particularly preferred polymers according to the invention are those in which D represents a value of 0, X represents a chlorine atom, and the molecular weight measured by carbon-13 NMR (C ¹³ NMR) is about 25 500 (V). Of polymers.
[293] According to the invention, the cationic polymer (s) represent approximately 0.01% to 10% by weight, preferably 0.05% to 5%, even more preferably 0.1% to 3%, relative to the total weight of the composition.
[294] Amphoteric polymers that can be used according to the invention can be selected from polymers comprising units K and M distributed randomly in the polymer chain, where K denotes units derived from monomers having at least one basic nitrogen atom and , M may represent a unit derived from an acid monomer having at least one carboxylic acid group or a sulfonic acid group, or alternatively K and M may represent a group derived from a carboxybetaine or sulfobetaine zwitterionic monomer;
[295] K and M may also represent cationic polymer chains having primary, secondary, tertiary or quaternary amine groups, wherein one or more amine groups have carboxylic acid groups or sulfonic acid groups linked via hydrocarbon-based radicals, or alternatively K and M, in turn, form part of a polymer chain having an α, β-dicarboxylic acid ethylene unit in which one or more carboxylic acid groups are reacted with a polyamine having one or more primary or secondary amine groups.
[296] More particularly preferred ampholytic polymers are selected from the following polymers:
[297] (1) more particularly monomers derived from vinyl compounds having carboxylic acid groups such as acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and more particularly dialkylaminoalkyl methacrylates and acrylates, dialkylamino A polymer resulting from the copolymerization of a basic monomer derived from a substituted vinyl compound comprising one or more basic atoms such as alkylmethacrylamide and -acrylamide. Such compounds are described in US Pat. 3 836 537. Mention may also be made of sodium acrylate / acrylamidopropyltrimethylammonium chloride copolymers sold under the name Polyquart KE 3033 by the company Henkel.
[298] Substituted vinyl compounds comprising one or more basic atoms may also be dialkyldiallylammonium salts such as dimethyldiallylammonium chloride. Copolymers of acrylic acid and the latter monomers are sold by Calgon under the names Merquat 280, Merquat 295 and Merquat Plus 3330.
[299] (2) a polymer comprising monomers derived from:
[300] a) at least one monomer selected from acrylamide and methacrylamide substituted by alkyl radicals on nitrogen,
[301] b) at least one acidic comonomer comprising at least one reactive carboxylic acid group, and
[302] c) one such as quaternization products of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate of esters containing primary, secondary, tertiary and quaternary amine substituents of acrylic acid and methacrylic acid Basic comonomers above.
[303] More particularly preferred N-substituted acrylamides or methacrylamides according to the invention are groups in which the alkyl radical comprises 2 to 12 carbon atoms, more particularly N-ethylacrylamide, N-tert-butylacrylamide, N -tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamide.
[304] Acidic comonomers are more particularly selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and alkyl monoesters having 1 to 4 carbon atoms, or maleic acid or fumaric acid or anhydrides.
[305] Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl and N-tert-butylaminoethyl methacrylate.
[306] Particularly used are copolymers whose CTFA (4th edition, 1991) name is octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer, such as those sold by National Starch under the name Amphomer or Lovocryl 47.
[307] (3) crosslinked and alkylated polyamino amides partially or wholly derived from polyamino amides having the general formula:
[308]
[309] [Wherein R ₁₈ is a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkanol having 1 to 6 carbon atoms of the acid, or in the acid Represents a divalent radical derived from a radical derived by addition of one to a bis (primary) or bis (secondary) amine, where Z is a bis (primary), mono- or bis (secondary) polyalkylene-polyamine Radicals are indicated and preferably the following:
[310] a) in the proportion of 60 to 100 mol%,
[311]
[312] Where x = 2, p = 2 or 3, or alternatively x = 3, p = 2
[313] This radical is derived from diethylenetriamine, triethylenetetraamine or dipropylenetriamine;
[314] b) in the proportion of 0 to 40 mol%, wherein said radical (VII) derived from ethylenediamine and x = 2, p = 1 and radicals derived from piperazine:
[315]
[316] c) —NH— (CH ₂ ) ₆ —NH—radicals derived from hexamethylenediamine in a ratio of 0 to 20 mol%], such polyamino amines include epihalohydrin, diepoxide, dianhydride and Crosslinked using 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide by addition of a bifunctional crosslinking agent selected from bis-unsaturated derivatives, and of acrylic acid, chloroacetic acid or alkane sultone, or salts thereof Alkylated by action.
[317] Saturated carboxylic acids are preferably acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid, for example acrylic acid, It is selected from acids containing ethylenic double bonds, such as methacrylic acid and itaconic acid.
[318] The alkane sultone used for alkylation is preferably propane sultone or butane sultone, and the salt of the alkylating agent is preferably the sodium or potassium salt.
[319] (4) a polymer comprising a zwitterionic unit of the formula:
[320]
[321] [Wherein, R ₂₃ represents a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer of 1 to 3, and R ₁₉ and R ₂₀ are hydrogen atoms , Methyl, ethyl or propyl, and R ₂₁ and R ₂₂ represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R ₂₁ and R ₂₂ does not exceed 10;
[322] Polymers comprising such units are also derived from non-zwitterionic monomers, such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylate or methacrylate, acrylamide or methacrylamide, or vinyl acetate. It may include units.
[323] By way of example, mention may be made of copolymers of butyl methacrylate / dimethyl carboxymethylammonio ethyl methacrylate, such as the product sold by Sandoz under the name Diaformer Z301.
[324] (5) a polymer derived from chitosan comprising monomer units corresponding to formulas IX, X and XI
[325]
[326] Unit (IX) is present at a rate of 0 to 30%, unit (X) is present at a rate of 5 to 50%, unit (XI) is present at a rate of 30 to 90%, and in unit (XI), R ₂₄ is Radicals of the formula
[327]
[328] [In the meal,
[329] When q = 0, R ₂₅ , R ₂₆ and R ₂₇ can be the same or different, each of which is hydrogen atom, methyl, hydroxyl, acetoxy or amino moiety, optionally one or more nitrogen atoms inserted and / or one or more amines , Monoalkylamine residue or dialkylamine residue optionally substituted by hydroxyl, carboxyl, alkylthio or sulfonic acid group, alkylthio residue in which the alkyl group has an amino residue, in which case among the radicals R ₂₅ , R ₂₆ and R ₂₇ At least one is a hydrogen atom;
[330] Or when q = 1, each of R ₂₅ , R ₂₆ and R ₂₇ represents a hydrogen atom], as well as salts formed by such compounds and bases or acids.
[331] (6) polymers derived from N-carboxyalkylation of chitosans such as N-carboxybutylchitosan or N-carboxymethylchitosan sold by Jan Dekker under the name "Evalsan".
[332] (7) Polymers corresponding to formula (XII) are described, for example, in French patent 1 400 366:
[333]
[334] [Wherein R ₃₂ represents a hydrogen atom, CH ₃ O, CH ₃ CH ₂ O or a phenyl radical, R ₂₈ represents a hydrogen or a lower alkyl radical such as methyl or ethyl and R ₂₉ represents a hydrogen or a lower alkyl radical For example methyl or ethyl, R ₃₀ is a lower alkyl radical such as methyl or ethyl, or the formula: -R ₃₁ -N (R ₂₉ ) ₂ (R ₃₁ is -CH ₂ -CH _2- , -CH _2- R ₂ represents a CH ₂ —CH ₂ — or —CH ₂ —CH (CH ₃ ) — group, and R ₂₉ has the meanings mentioned above, as well as the higher analogs of these radicals, It contains carbon atoms.
[335] r has a molecular weight of 500 to 6 000 000, preferably 1 000 to 1 000 000].
[336] (8) amphoteric polymers of the type -D-X-D-X selected from:
[337] a) a polymer obtained by the action of chloroacetic acid or sodium chloroacetate on a compound comprising at least one unit of the formula:
[338] -D-X-D-X-D- (XIII)
[339] [Wherein D represents the radical:
[340]
[341] X represents the symbol E or E ', E or E' may be the same or different and is an alkylene radical comprising a straight or branched chain containing up to 7 carbon atoms in the main chain, and a hydroxyl group Denotes a divalent radical which is unsubstituted or substituted and, in addition to oxygen, nitrogen and sulfur atoms, may contain 1-3 aromatic and / or heterocyclic rings; Oxygen, nitrogen and sulfur atoms are ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester And / or in the form of a urethane group.
[342] b) a polymer of the formula:
[343] -D-X-D-X- (XIV)
[344] [Wherein D represents a radical of
[345]
[346] X represents the symbol E or E 'and at least once E'; E has the meaning given above, and E 'is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, unsubstituted or substituted with one or more hydroxyl radicals, and contains one or more nitrogen atoms Is a divalent radical, and the nitrogen atom is substituted with an alkyl chain which is optionally inserted with an oxygen atom and essentially contains one or more carboxyl functional groups or one or more hydroxyl functional groups, and is betained by the reaction of chloroacetic acid or sodium chloroacetate. ].
[347] (9) partially modified by semiamidation with N, N-dialkylaminoalkylamines such as N, N-dimethylaminopropylamine or semiesterification with N, N-dialkanolamine (C ₁ -C ₅ ) alkyl vinyl ether / maleic anhydride copolymer. Such copolymers may also include other vinyl comonomers such as vinylcaprolactam.
[348] Particularly preferred ampholytic polymers according to the invention are those of group (1).
[349] According to the invention, the amphoteric polymer (s) represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight and even more preferably from 0.1% to 3% by weight relative to the total weight of the composition. Can be.
[350] Polymers other than those useful in the present invention, which are amphiphilic and comprise one or more hydrocarbon chains, are also known as associative polymers; These may be of the nonionic, anionic or cationic type.
[351] Among amphiphilic polymers comprising at least one hydrocarbon chain and of anionic type, mention may be made of:
[352] (I) those comprising at least one hydrophilic unit and at least one allyl ether unit comprising a hydrocarbon chain, more particularly the hydrophilic unit being an ethylenically unsaturated anionic monomer, even more particularly vinylcarboxylic acid, most particularly acrylic acid Those consisting of methacrylic acid or mixtures thereof, wherein the allyl ether unit comprises a hydrocarbon chain corresponding to the monomer of formula (XV):
[353] CH ₂ = CR'CH ₂ OB _n R (XV)
[354] [Wherein R 'represents H or CH ₃ , B represents an ethyleneoxy radical, n represents 0 or an integer ranging from 1 to 100, and R represents alkyl, arylalkyl, aryl, alkyl Hydrocarbon-based radicals selected from aryl and cycloalkyl radicals and comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms, more particularly from 12 to 18 carbon atoms. More particularly preferred units of formula XV are those wherein R 'represents H, n is equal to 10 and R represents a stearyl ( _C18 ) radical.
[355] Anionic amphiphilic polymers of this type are described and prepared according to the emulsion polymerization method in patent EP-0 216 479.
[356] Of these hydrocarbon-chain anionic polymers, particularly preferred according to the invention are 20% to 60% by weight acrylic and / or methacrylic acid, 5% to 60% by weight lower alkyl (meth) acrylate, 2% by weight. Allyl ethers comprising from% to 50% by weight of hydrocarbon chains of formula XV and from 0% to 1% by weight of known copolymerizable unsaturated polyethylene-based monomers such as diallyl phthalate, allyl (meth) acrylate, divinyl Polymers formed from crosslinking agents that are benzene, (poly) ethylene glycol dimethacrylate or methylenebisacrylamide.
[357] Among the latter polymers, most particularly preferred are crosslinked terpolymers of methacrylic acid, ethyl acrylate and polyethylene glycol (10 EO) stearyl ether (Steareth-10), in particular methacrylic acid, ethyl acrylate and stearate. Sold under the names Salcare SC 80 and Salcare SC 90 by the company Allied Colloids, an aqueous 30% emulsion of crosslinked terpolymers of let-10 allyl ether (40/50/10).
[358] (II) hydrophilic units of at least one unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of a (C ₁₀ -C ₃₀ ) alkyl ester of an unsaturated carboxylic acid type.
[359] Preferably, such polymers have hydrophilic units of the unsaturated olefinic carboxylic acid type corresponding to monomers of formula XVI:
[360] [Formula XVI]
[361]
[362] Wherein R ₁ represents H or CH ₃ or C ₂ H ₅ , ie acrylic acid, methacrylic acid or ethacrylic acid units], hydrophobicity of the (C ₁₀ -C ₃₀ ) alkyl ester of the unsaturated carboxylic acid type The unit is selected from those corresponding to monomers of the formula XVII:
[363] Formula XVII]
[364]
[365] [Wherein R ₂ is H or CH ₃ or C ₂ H ₅ (ie acrylate, methacrylate or ethacrylate units), preferably H (acrylate units), or CH ₃ (methacrylate units) ) And R ₃ represents a C ₁₀ -C ₃₀ and preferably C ₁₂ -C ₂₂ alkyl radical.
[366] The (C ₁₀ -C ₃₀ ) alkyl esters of the unsaturated carboxylic acids according to the invention are, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and corresponding Methacrylates such as lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
[367] Anionic polymers of this type are described and prepared according to, for example, US Pat. Nos. 3 915 921 and 4 509 949.
[368] More particularly among these types of fat-chain anionic polymers are polymers formed from monomer mixtures containing:
[369] (i) essentially acrylic acid,
[370] (ii) an ester of formula (XVI) as described above wherein R ₂ represents H or CH ₃ and R ₃ represents an alkyl radical comprising 12 to 22 carbon atoms,
[371] and (iii) and known copolymerizable polyethylene-based unsaturated monomers such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylenebisacrylamide.
[372] Among the fat-chain anionic polymers of this type more particularly used are 95% to 60% by weight of acrylic acid (hydrophilic units), 4% to 40% by weight of C ₁₀ -C ₃₀ alkyl acrylates (hydrophobic units) and 0 Consisting of weight percent to 6 weight percent crosslinkable polymerizable monomer, or alternatively 98 weight percent to 96 weight percent acrylic acid (hydrophilic units), 1 weight percent to 4 weight percent C ₁₀ -C ₃₀ alkyl acrylate (Hydrophobic unit) and 0.1% to 0.6% by weight of crosslinkable polymerizable monomer as described above.
[373] Among the polymers mentioned above, the most particularly preferred according to the invention are the products sold under the trade names Pemulen TR1, Pemulen TR2 and Carbopol 1382 by the company Goodrich, and more preferably under the name Coatex SX by the company SEPPIC. It is a product sold.
[374] (III) maleic anhydride / C ₃₀ -C ₃₈ α-olefin / alkyl maleate terpolymers, such as the product sold by Newphase Technologies under the name Performa V 1608 (maleic anhydride / C ₃₀ -C ₃₈ α-olefin / Isopropyl maleate copolymer).
[375] (IV) an acrylic acid terpolymer containing:
[376] (a) about 20% to 70% by weight of a carboxylic acid comprising α, β-monoethylenic unsaturation,
[377] (b) about 20% to 80% by weight of a non-surfactant monomer comprising α, β-monoethylenic unsaturation other than (a),
[378] (c) about 0.5% to 60% by weight of a nonionic monourethane which is the product of the reaction of a monovalent surfactant with a monoisocyanate comprising monoethylenic unsaturation,
[379] For example, as an aqueous 25% dispersion, those described in patent application EP-A-0 173 109, more particularly the terpolymers described in Example 3, ie methacrylic acid / methyl acrylate / behenyl dimethyl-meth-iso Propenylbenzylisocyanate ethoxylated (40 EO) terpolymer.
[380] (V) carboxylic acids comprising α, β-monoethylenic unsaturation, and carboxylic acids comprising α, β-monoethylenic unsaturation and (C ₈ -C ₃₀ ) oxyalkylenated hydrocarbons in its monomers Copolymers comprising esters of alcohols.
[381] Preferred such compounds also include esters of carboxylic acids and C ₁ -C ₄ alcohols comprising α, β-monoethylenic unsaturations as monomers.
[382] One example of this type of compound that may be mentioned is Aculyn 22, sold by Rohm & Haas, a methacrylic acid / ethyl acrylate / stearyl methacrylate oxyalkylenated terpolymer.
[383] Fatty-chain amphiphilic polymers of the nonionic type used according to the invention are preferably selected from:
[384] (1) cellulose modified with a group comprising at least one hydrocarbon chain;
[385] Examples that may be mentioned include:
[386] Hydroxyethylcellulose modified with a group comprising at least one hydrocarbon chain, such as an alkyl, arylalkyl or alkylaryl group, or mixtures thereof, wherein the alkyl group is preferably C ₈ -C ₂₂ , for example from Aqualon Products sold by Natrosol Plus Grade 330 CS (C ₁₆ alkyl), or products sold by Berol Nobel. Bermocoll EHM 100.
[387] Modified by alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500 (nonylphenyl polyethylene glycol (15) ether) sold by the company Amerchol.
[388] (2) hydroxypropylguar modified with a group comprising at least one hydrocarbon chain, such as product Esaflor HM 22 (C ₂₂ alkyl chain) sold by Lamberti, and product RE210-18 sold by Rhone-Poulenc C ₁₄ alkyl chains) and RE205-1 (C ₂₀ alkyl chains).
[389] (3) copolymers of vinylpyrrolidone and fat-chain hydrophobic monomers;
[390] Examples that may be mentioned include:
[391] Antaron V216 or Ganex V216 (vinylpyrrolidone / hexadecene copolymer) sold by I.S.P.
[392] -Products Antaron V220 or Ganex V220 (vinylpyrrolidone / eicosene copolymer) sold by I.S.P.
[393] (4) C ₁ -C ₆ alkyl methacrylates or copolymers of acrylates and amphiphilic monomers comprising at least one hydrocarbon chain, for example oxyethylenated methyl sold by Goldschmidt under the name Antil 208 Acrylate / stearyl acrylate copolymer.
[394] (5) copolymers of hydrophilic methacrylates or acrylates with hydrophobic monomers comprising at least one hydrocarbon chain, for example polyethylene glycol methacrylate / lauryl methacrylate copolymers.
[395] (6) polymers having an aminoplast ether skeleton comprising at least one hydrocarbon chain, such as Pure Thix compounds sold by Sud-Chemie.
[396] (7) a polyurethane polyether comprising in its chain both hydrophilic blocks of predominantly polyoxyethylenated nature and hydrophobic blocks which may be aliphatic sequences alone and / or alicyclic and / or aromatic sequences,
[397] Preferably, it comprises at least two hydrocarbon-based lipophilic chains containing 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chain being a pendant chain, or a chain at the end of a hydrophilic block Phosphorus polyether polyurethane. In particular, it is possible for one or more pendant chains to be included. In addition, the polymer may comprise a hydrocarbon-based chain at one or both ends of the hydrophilic block.
[398] The polyether polyurethanes may be in the form of multiblocks, in particular triblocks. The hydrophobic blocks can be at each end of each chain (eg: 3 block copolymers of hydrophilic central blocks), or can be distributed at the ends and chains (eg: multiblock copolymers). These same polymers may also be graft polymers or starburst polymers.
[399] The nonionic fatty-chain polyether polyurethane may be a three block copolymer wherein the hydrophilic block is a polyoxyethylenated chain containing 50 to 1 000 oxyethylene groups. Nonionic polyether polyurethanes include urethane linkages between hydrophilic blocks, from which the name derives.
[400] Broadly speaking, nonionic fatty-chain polyether polyurethanes also include those in which the hydrophilic block is linked to other lipophilic blocks via other chemical bonds.
[401] Examples of nonionic fatty-chain polyether polyurethanes used in the present invention are also sold by Rheox, Inc., Rheolate 205 or Rheolates 208, 204 or 211, including urea functionality, and also sold by Rohm & Haas. Acrysol RM 184, Aculyn or Acrysol 44 and Aculyn or Acrysol 46, wherein 15% by weight to 150 or 180 mol of ethylene oxide, stearyl alcohol in a matrix of maltodextrin (4%) and water (81%) And methylenebis (4-cyclohexyl isocyanate) (SMDI); a condensation polymer of polyethylene glycol; Aculyn 44 comprises 35 to 150 or 180 mol of ethylene oxide, decyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI) in a matrix of propylene glycol (39%) and water (26%). Polycondensates of polyethylene glycols.
[402] Mention may also be made of Akzo, articles Elfacos T210 comprising a C _12-14 alkyl chain, and articles Elfacos T212 comprising a C ₁₈ alkyl chain.
[403] The product DW 1206B from Rohm & Haas, including C ₂₀ alkyl chains and urethane linkages, sold at 20% solids content in water, can also be used.
[404] It is also possible to use solutions or dispersions of such polymers, especially in water or aqueous-alcoholic media. Examples of such polymers which may be mentioned are Rheolate 255, Rheolate 278 and Rheolate 244 sold by Rheox. The products DW 1206F and DW 1206J sold by Rohm & Haas may also be used.
[405] Polyether polyurethanes which can be used according to the invention are in particular G. Fonnum, J. Bakke and Fk. By Hansen-[Colloid Polym. Sci 271, 380.389 (1993).
[406] As used herein, an amphiphilic polymer of cationic type comprising at least one hydrocarbon chain is preferably selected from polyacrylates and quaternized cellulose derivatives comprising acrylic amino side groups.
[407] Quaternized cellulose derivatives, in particular,
[408] Quaternized celluloses modified with groups comprising at least one hydrocarbon chain, such as alkyl, aralkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.
[409] Quaternized hydroxyethylcellulose modified with groups comprising at least one hydrocarbon chain, such as alkyl, aralalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.
[410] The alkyl radical contained in the quaternized cellulose or hydroxyethyl cellulose preferably contains 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
[411] Examples of quaternized alkylhydroxyethylcelluloses containing C ₈ -C ₃₀ hydrocarbon chains that may be mentioned include the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529 sold by Amerchol. -18B (C ₁₂ alkyl) and Quatrisoft LM-X 529 8 (C ₁₈ alkyl) and products sold by Croda Corporation Crodacel QM, Crodacel Ql (C ₁₂ alkyl) and Crodacel QS (C ₁₈ alkyl).
[412] Polyacrylates comprising quaternized or unquaternized amino side groups include, for example, hydrophobic groups of the type such as Steareth 20 (polyoxyethylenated (20) stearyl alcohol).
[413] Examples of polyacrylates comprising amino side chains, which may be mentioned, include polymers 8781-121B and 9492-103 sold by National Starch.
[414] In the oxidation dye composition according to the invention, it is preferable to use, among the fat-chain amphiphilic polymers, amphiphilic polymers of nonionic or cationic type comprising at least one hydrocarbon chain.
[415] According to the present invention, the amphiphilic polymer (s) comprising one or more hydrocarbon chains may represent from about 0.01% to 10% by weight relative to the total weight of the composition. Preferably, this amount is in the range of about 0.1% to 5% by weight.
[416] Needless to say, those skilled in the art carefully select these optional additional compound (s) so that they are adversely affected by the additional (s) contemplated by the beneficial properties essentially associated with the oxidative dye composition according to the invention. Unaffected or substantially unaffected.
[417] The dye compositions according to the invention can be in various forms, such as liquids, creams or gels or keratin fibres, in particular any other form suitable for dyeing human hair.
[418] Subject of the invention is also a method of dyeing keratin fibers, in particular human keratin fibers, such as hair, using a dye composition as defined above.
[419] According to this method, one or more dye compositions as defined above are applied to the fibers and added to the dye composition in use, or are acidic, neutral or alkaline pH with the aid of the oxidizing agent present in the oxidizing composition applied simultaneously or sequentially. Color appears.
[420] According to a preferred embodiment of the dyeing process of the present invention, the dye composition described above is preferably mixed in use with an oxidizing composition comprising at least one oxidant present in a medium suitable for dyeing in an amount sufficient to cause coloring. do. The resulting mixture is then applied to the keratinous fibers and left to remain on the fibers for approximately 3 to 50 minutes, preferably approximately 5 to 30 minutes, after which the fibers are rinsed, washed with shampoo, rinsed again and dried .
[421] The oxidizing agent can be chosen among the oxidizing agents which are commonly used for the oxidative staining of keratin fibers, among which mention may be made of perchlorates, peracids and enzymes such as hydrogen peroxide, urea peroxide, alkali metal bromate, perborate and persulfate Among the enzymes, mention may be made of peroxidases, two-electron redoxases such as freecases, and four-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.
[422] The pH of the oxidizing composition containing an oxidizing agent as defined above is preferably about 3-12, more preferably 5-11, of the resulting composition, which is applied to the keratinous fibers after mixing with the dye composition. Is the value that causes It is mainly used for dyeing keratin fibers and adjusted to the desired value with the aid of an acidifying or basicizing agent as defined above.
[423] Oxidizing compositions, as defined above, may also contain various adjuvants, as commonly used in compositions for dyeing hair, and as defined above.
[424] The composition finally applied to the keratinous fibers may be in various forms, such as liquids, creams or gels, or any other form suitable for dyeing keratinous fibers, especially human hair.
[425] Another subject matter of the invention is a multicompartment dye "kit" or any other wherein the first compartment comprises a dye composition as defined above and the second compartment comprises an oxidizing composition as defined above. Compartment packing system. Such a device may be equipped with means for transferring the desired mixture to the hair, such as the device described in Applicant's patent FR-2 586 913.
[426] Finally, the subject matter of the present invention also relates to formula (I) as defined above in the presence of one or more oxidizing agents as defined above, and optionally in the presence of one or more coupling agents and / or one or more selective oxidation bases. A colored product resulting from the oxidation of a compound of.
[427] Such colored products may in particular be in the form of pigments and may be used as direct dyes for the direct dyeing of hair, or alternatively, may be included in cosmetic products, for example makeup products.
[428] The following examples are intended to illustrate the present invention.
[429] Synthetic Example
[430] Example 1: (4-amino-3-methylphenyl) pyrrolidin-3-ylamine dihydrochloride (3)
[431]
[432] Synthesis of N- [1- (3-methyl-4-nitrophenyl) pyrrolidin-3-yl] acetamide (1):
[433] Dissolve 15.5 g of 5-fluoro-2-nitrotoluene (0.1 mol) and 12.8 g of 3-acetamidopyrrolidine (0.1 mol) in 75 mL of NMP, followed by 15.8 g of potassium carbonate (0.12 mol). Add under nitrogen atmosphere and heat the mixture at 95 ° C. for 20 hours. The reaction medium is cooled and then poured into 600 ml of saturated aqueous sodium chloride solution. The yellow precipitate formed is filtered off, washed with 15% NaCl solution until the pH of the wash water reaches 7, washed with petroleum ether and then dried in a vacuum oven on P ₂ O ₅ . This gives 25.7 g (98%) of N- [1- (3-methyl-4-nitrophenyl) pyrrolidin-3-yl] acetamide in the form of a yellow solid.
[434] Synthesis of 1- (3-methyl-4-nitrophenyl) pyrrolidin-3-ylamine (2)
[435] 24 g (0.0911 mol) of N- [1- (3-methyl-4-nitrophenyl) pyrrolidin-3-yl] acetamide (1) was dissolved in 75 ml of 37% hydrochloric acid in a 500 ml three-neck flask and It is introduced into a solution containing 165 ml of water. The reaction medium is heated at 90 ° C. for 2 hours 30 minutes. After cooling, the medium is carefully neutralized with 75 ml of 35% aqueous sodium hydroxide (pH = about 8). The resulting solid is then filtered off and washed with water until the wash water is neutral. The product is then dried under vacuum on P ₂ O ₅ . This gives 16.8 g (83%) of 1- (3-methyl-4-nitrophenyl) pyrrolidin-3-ylamine (2) in the form of a yellow solid.
[436] Synthesis of (4-amino-3-methylphenyl) pyrrolidin-3-ylamine dihydrochloride (3)
[437] Partially dissolve 16 g of 1- (3-methyl-4-nitrophenyl) pyrrolidin-3-ylamine (2) (72.3 mmol) in 320 ml of 96 ° ethanol in a stainless-steel hydrogenation reactor. . 4 g of 5% Pd / C (50% water) is added and the reactor is closed and purged three times with nitrogen while stirring (1,600 rpm). Hydrogen is then introduced at a pressure of 5-6 bar at ambient temperature. The temperature rises to 35 ° C. and then falls back to 27 ° C. over 1 hour. The reactor is then purged with nitrogen, the reaction medium is filtered under a nitrogen atmosphere and the filtrate is soon recovered in a solution containing 27 ml of 37% hydrochloric acid and 200 ml of isopropanol. The filtrate is then concentrated until a precipitate is obtained. The solid is filtered off, washed with isopropanol and then ethyl ether and dried under vacuum in the presence of potassium hydroxide. This gives 15 g (78%) of (4-amino-3-methylphenyl) pyrrolidin-3-ylamine dihydrochloride (3) in the form of a white solid. ^{The 1} H-NMR spectrum and the mass spectrum are consistent with the spectrum of product (3).
[438] Elemental Analysis (MW = 264.198; C ₁₁ H ₁₇ N ₃ · 2HCl)
[439] % C% H% N% Cl Theory50.017.2515.926.84 Found48.297.8414.2324.37
[440] Example 2: 1- (4-amino-3-methoxyphenyl) pyrrolidine-3-ol-dihydrochloride (3)
[441]
[442] Synthesis of 4-fluoro-2-methoxy-1-nitrobenzene (1):
[443] 25 g (0.159 mol) of 5-fluoro-2-nitrophenol are added to 125 ml of DMSO. 22.5 g (0.159 mol) of methyl iodide are then added, followed by the dropwise addition of 17.8 g of 50% aqueous potassium hydroxide solution while maintaining the temperature below 25 ° C. After the mixture is stirred at ambient temperature for 1 hour, 22.5 g (0.159 mol) of methyl iodide are further added. After stirring for 24 hours, the reaction medium is poured into 125 ml of water and then extracted with 60 ml of dichloromethane. The organic phase is washed with 90 ml of aqueous sodium hydroxide solution (1N) followed by 60 ml of water. After drying the MgSO ₄ phase, the organic phase is concentrated under reduced pressure. Thus, 20.59 g (76%) of 4-fluoro-2-methoxy-1-nitrobenzene (1) is recovered.
[444] Synthesis of 1- (3-methoxy-4-nitrophenyl) pyrrolidin-3-ol (2):
[445] 8 g (46 mmol) of 4-fluoro-2-methoxy-1-nitrobenzene (1), 80 ml of dioxane and 8.14 g (0.095 mol) of (R)-(+)-3-pyrroli Each diol is placed in a reactor. The mixture is refluxed for 1 hour. The reaction medium is poured into a mixture of water (100 ml) -ice (200 g). A yellow product precipitates out. This product is filtered off, washed with water (3 x 30 ml) and dried under vacuum at 45 < 0 > C. Thus, 8.38 g (75%) of 1- (3-methoxy-4-nitrophenyl) pyrrolidin-3-ol (2) is recovered.
[446] Synthesis of 1- (4-amino-3-methoxyphenyl) pyrrolidin-3-ol dihydrochloride (3):
[447] 12 g (0.05 mol) 1- (3-methoxy-4-nitrophenyl) pyrrolidin-3-ol (2), 36 ml ethanol, 24 ml cyclohexene and 5.4 g 10% Pd / C (50% water) are each added to the reactor, and then the reaction medium is refluxed for 5 hours. The medium is then filtered through Celite and the filtrate is collected on 5N hydrochloric ethanol solution. Celite is washed with ethanol (3 x 20 ml). The organic phases are combined and concentrated until a yellow precipitate appears. After cooling to 0 ° C. and stirring for 1 h, the product is filtered, rinsed with water and dried under vacuum. 10.5 g (74.1%) of 1- (4-amino-3-methoxyphenyl) pyrrolidone-3-ol dihydrochloride (3) is thus recovered in the form of a pale orange solid. ^{The 1} H-NMR spectrum and the mass spectrum are consistent with the spectrum of product (3).
[448] Elemental Analysis (MW = 281.181; C ₁₁ H ₁₆ N ₂ O ₂ · 2HCl)
[449] % C% H% N% O% Cl Theory46.996.459.9611.3825.25 Found46.886.839.5811.2824.98
[450] Example 3: (R) -1- (4-aminophenyl) pyrrolidine-3-ol dihydrochloride (2)
[451]
[452] Synthesis of (R) -1- (4-aminophenyl) pyrrolidin-3-ol dihydrochloride (2):
[453] Under a gentle flow of nitrogen, 200 ml stainless-steel hydrogenation fully equipped with 5 g (24 mmol) of (R) -1- (4-nitrophenyl) pyrrolidin-3-ol and 1 g of palladium on activated carbon Is introduced into the reactor. 50 ml of ethanol are then added, blown three times with nitrogen and once with hydrogen and the mixture is stirred at 1 500 rpm. Hydrogen is then introduced under a pressure of 5.5 bar. It generates heat and reaches 55 ° C. After 1 hour 30 minutes, the temperature drops back to 31 ° C. The mixture is purged under nitrogen and then filtered through a waste filter under nitrogen pressure of 2 bar. The filtrate is recovered in an ice cold mixture of 7 ml concentrated hydrochloric acid and 21 ml isopropanol. The partially crystalline mixture is transferred to a round bottom flask with 20 ml of additional isopropanol and then the isopropanol is evaporated under reduced pressure. After concentration, the product is sufficiently crystallized. Next, 40 ml of isopropanol are added, gently flushed with nitrogen and the compound is allowed to stir overnight. The mixture is then filtered, spin-filtered, washed with 20 ml of isopropanol and dried at a temperature of 40 ° C. under high vacuum (˜10 mmHg). This gives 4.3 g (71%) of (R) -1- (4-aminophenyl) pyrrolidin-3-ol dihydrochloride (2). ^{The 1} H-NMR spectrum and the mass spectrum correspond to the spectrum of the product (3).
[454] % C% H% N% O% Cl Theory47.826.8211.156.3728.23 Found47.276.4011.066.9927.95
[455] Example 4: N- [1- (4-aminophenyl) pyrrolidin-3-yl] acetamide dihydrochloride (2)
[456]
[457] Synthesis of N- [1- (4-nitrophenyl) pyrrolidin-3-yl] acetamide (1):
[458] 56.4 g of 1-fluoro-4-nitrobenzene (0.4 mol) and 51.2 g of 3-acetamidopyrrolidine (0.4 mol) are dissolved in 400 ml of NMP, followed by 66.4 g of potassium carbonate (0.48 mol) Is added under hydrogen atmosphere and the mixture is heated at 100 ° C. for 18 h. After cooling the reaction medium, it is poured into 2 l of water. The yellow precipitate formed is filtered off, washed with water and then dried in a vacuum oven over P ₂ O ₅ . Thus, 100 g (100%) of N- [1- (4-nitrophenyl) pyrrolidin-3-yl] acetamide (1) is obtained in the form of a yellow solid.
[459] Synthesis of N- [1- (4- (aminophenyl) pyrrolidin-3-yl] acetamide monohydrochloride (2):
[460] 30 g of N- [1- (4-nitrophenyl) pyrrolidin-3-yl] acetamide (1) (120 mmol) is partially dissolved in 670 ml of absolute ethanol in a stainless-steel hydrogenation reactor. 4.5 g of 5% Pd / C (50% water) is added and the reactor is closed and purged three times with nitrogen with stirring (1 600 rpm). Hydrogen is then introduced at a pressure of 10 bar at ambient temperature. The reaction medium is heated to 55 ° C. and then cooled to 27 ° C. over 3 hours. The reactor is then purged with nitrogen, the reaction medium is filtered under a nitrogen atmosphere and the filtrate is immediately recovered in 90 ml of hydrochloric ethanol solution (5N). The filtrate is then concentrated until a precipitate is obtained. The solid is filtered off, washed with isopropanol and then ethyl ether and dried under vacuum in the presence of potassium hydroxide. This gives 19.4 g (63%) of N- [1- (4-aminophenyl) pyrrolidin-3-yl] acetamide dihydrochloride (2) in the form of a white solid. ^{The 1} H-NMR spectrum and the mass spectrum are consistent with the spectrum of product (2).
[461] Elemental Analysis (MW = 292.208; C ₁₂ H ₁₇ N ₃ O.2HCl)
[462] % C% H% N% O% Cl Theory49.336.5514.385.4824.27 Found48.356.6214.197.1720.52
[463] Example 5: [1- (4-aminophenyl) pyrrolidin-3-yl] dimethylamine dihydrochloride (2)
[464]
[465] Synthesis of Dimethyl- [1- (4-nitrophenyl) pyrrolidin-3-yl] amine (1):
[466] 32.28 g of potassium carbonate (308 mmol) is added to a 250 ml aqueous solution containing 29.3 g of N, N-dimethylaminopyrrolidine (257 mmol) and 36.23 g of 4-fluoronitrobenzene (257 mmol) After that, the mixture is refluxed for 3 hours. The reaction medium is dissolved and then the product precipitates. The product is filtered off and washed with water. It is dried in a vacuum oven at 40 ° C. on P ₂ O ₅ . This gives 55.9 g (92%) of dimethyl- [1- (4-nitrophenyl) pyrrolidin-3-yl] amine (1) in the form of a yellow solid.
[467] Synthesis of [1- (4-aminophenyl) pyrrolidin-3-yl] dimethylamine dihydrochloride (2):
[468] 50 g of dimethyl- [1- (4-nitrophenyl) pyrrolidin-3-yl] amine (1) (212 mmol) are added to 500 ml of absolute ethanol in a stainless-steel hydrogenation reactor. 10 g of 5% Pd / C (50% of water) is added and the reactor is closed and purged three times with nitrogen while stirring (1 600 rpm). Hydrogen is then introduced at a pressure of 5-6 bar at ambient temperature. The temperature rises to 35 ° C. and falls back to 27 ° C. over 1 hour. The reactor is then purged with nitrogen, the reaction medium is filtered under a nitrogen atmosphere and the filtrate is immediately recovered in a solution containing 62 ml of 37% hydrochloric acid and 240 ml of isopropanol. The filtrate is then concentrated until a precipitate is obtained. The solid is filtered off, washed with isopropanol and then ethyl ether and dried at 50 ° C. in the presence of potassium hydroxide under vacuum. This gives 39.1 g (66%) of [1- (4-aminophenyl) pyrrolidin-3-yl] dimethylamine dihydrochloride (2) in the form of a white solid. ^{The 1} H-NMR spectrum and the mass spectrum match the spectrum of the product.
[469] Elemental Analysis (MW = 278.225; C ₁₂ H ₁₉ N ₃ .2HCl)
[470] % C% H% N% Cl Theory51.87.6115.125.49 Found51.27.7314.8325.46
[471] Example 6: 1- (4-aminophenyl) pyrrolidin-3-ylamine dihydrochloride (3)
[472]
[473] Synthesis of N- [1- (4-nitrophenyl) pyrrolidin-3-yl] acetamide (1):
[474] 56.4 g of 1-fluoro-4-nitrobenzene (0.4 mol) and 51.2 g of 3-acetamidopyrrolidine (0.4 mol) are dissolved in 400 ml of NMP, followed by 66.4 g of potassium carbonate (0.48 mol) Is added under nitrogen atmosphere and the mixture is heated at 100 ° C. for 18 h. After cooling the reaction medium, it is poured into 2 l of water. The resulting yellow precipitate is filtered off, washed with water and dried in a vacuum oven on P ₂ O ₅ . Thus, 100 g (100%) of N- [1- (4-nitrophenyl) pyrrolidin-3-yl] acetamide (1) is obtained in the form of a yellow solid.
[475] Synthesis of 1- (4-nitrophenyl) pyrrolidin-3-ylamine (2):
[476] 100 g (0.4 mol) of N- [1- (4-nitrophenyl) pyrrolidin-3-yl] acetamide (1) as a suspension, 300 ml of 37% hydrochloric acid and 660 ml in a 2 l three-neck flask It is introduced into a solution containing water. The reaction medium was heated at 90 ° C. for 7 hours 45 minutes. After cooling, the medium is carefully neutralized with 300 ml of 35% aqueous sodium hydroxide (pH = about 8). The resulting solid is then filtered and washed with water (until the wash water is neutral). The product is then dried in a vacuum oven on P ₂ O ₅ . This gives 74 g (89%) of 1- (4-nitrophenyl) pyrrolidin-3-ylamine (2) in the form of a yellow solid.
[477] Synthesis of 1- (4-aminophenyl) pyrrolidin-3-ylamine dihydrochloride (3):
[478] 72 g of 1- (4-nitrophenyl) pyrrolidin-3-ylamine (2) (347 mmol) is added to 600 ml of methanol in a stainless-steel hydrogenation reactor. 15 g of 5% Pd / C (50% water) is added and the reactor is closed and purged with nitrogen three times with stirring (1 600 rpm). Hydrogen is then introduced at a pressure of 5 bar at ambient temperature. The temperature rises to 52 ° C. and then falls back to 38 ° C. over 2 hours 50 minutes. The reactor is then purged with nitrogen and the reaction medium is filtered under a nitrogen atmosphere and the filtrate is immediately recovered in a solution containing 130 ml of 37% hydrochloric acid, 200 ml of isopropanol and 200 ml of anhydrous ethanol. The filtrate is then concentrated until a precipitate is obtained. The solid is filtered off, washed with isopropanol and then ethyl ether and dried under vacuum at 50 ° C. in the presence of potassium hydroxide. This gives 71 g (82%) of 1- (4-aminophenyl) pyrrolidin-3-ylamine dihydrochloride (3) in the form of a white solid. ^{The 1} H-NMR spectrum and the mass spectrum are consistent with the product (3).
[479] Elemental Analysis (MW = 250.171; C ₁₀ H ₁₅ N ₃ .2HCl)
[480] % C% H% N% Cl Theory48.016.8516.828.34 Found46.336.7816.528.97
[481] Example 7: Synthesis of 1- (4-aminophenyl) pyrrolidin-3-ol hydrochloride
[482]
[483] Step 1: Preparation of 1- (4-nitrophenyl) pyrrolidin-3-ol
[484] 2 g of 1-fluoro-4-nitrobenzene (0.0155 mol), 1.3 g sodium hydrogencarbonate (0.0155 mol) and 15 ml dioxane / water (8/2) mixture were introduced into a three neck flask. 1.35 g of racemic 3-pyrrolidinol (0.0155 mol) was quickly added to this mixture. The heterogeneous mixture was refluxed (87 ° C.) for 10 hours. Then the reaction mixture was poured into ice cold water; A yellow precipitate was obtained which was filtered off and rinsed with water. After drying in vacuo in the presence of P ₂ O ₅ , 2.95 g of a yellow solid were obtained (yield 97%).
[485] ¹ H-NMR analysis (DMSO-d ₆ , 200 MHz, 2H) according to the desired product was as follows:
[486] 8.04 (d, J = 9 Hz, 2H); 6.58 (d, J = 9 Hz, 2H); 5.06 (d, J = 3.6 Hz, 1 H); 4.41 (m, 1 H); 3.45 (m, 3 H); 3.20 (m, 1 H); 2.04 (m, 2 H).
[487] Elemental analysis was as follows:
[488] %CHNO Theory57.895.8113.4523.05 Found57.175.7213.2323.28
[489] Step 2: Preparation of 1- (4-aminophenyl) pyrrolidin-3-ol hydrochloride
[490] 1- (4-aminophenyl) pyrrolidin-3-ol (2 g, 9.605 mmol) obtained in the previous step was charged with 40 ml of anhydrous ethanol and 8 ml in the presence of 1 g of wet activated carbon-phase-palladium. Suspended in cyclohexene. Argon was then bubbled into the reaction medium for several minutes and then refluxed for 4 hours. The reaction mixture was filtered into a vacuum flask cooled to −5 ° C. containing 100 ml of diisopropyl ether, 50 ml of isopropanol and 4 equivalents of hydrochloric ethanol (6.2 ml). The precipitate obtained was quickly filtered and dried at 30 ° C. in a vacuum oven. Yield of 59% yielded 1.22 g of pale pink solid with melting point above 200 ° C.
[491] ¹ H-NMR analysis (MeOH-d ₄ , 200 MHz, ppm) according to the desired product was as follows:
[492] 7.26 (d, J = 9 Hz, 2H); 7.08 (d, J = 9 Hz, 2H), 4.48 (m, 1H); 3.54 (m, 3 H); 3.30 (m, 1 H); 2.09 (m, 2 H).
[493] Elemental analysis was as follows:
[494] %CHNOCl Theory48.186.7011.249.6424.23 Found48.546.6211.16924.67
[495] The product obtained contains 1.7 moles of HCl and 0.5 moles of water.
[496] Example 8: Synthesis of 1- (4-amino-2-methylphenyl) pyrrolidine-3-ol hydrochloride
[497]
[498] Step 1: Preparation of 1- (4-nitro-2-methylphenyl) pyrrolidin-3-ol
[499] 2.4 g of 1-fluoro-2-methyl-4-nitrobenzene (0.0155 mol), 1.3 g of sodium bicarbonate (0.0155 mol) and 15 ml of dioxane / water (8/2) mixture were added to a three neck flask. Introduced. 1.35 g of racemic 3-pyrrolidinol (0.0155 mol) was quickly added to this mixture. The heterogeneous mixture was refluxed (87 ° C.) for 24 hours. The reaction mixture is then poured into ice cold water; An orange precipitate was obtained, which was filtered and rinsed with water. After drying in vacuo in the presence of P ₂ O ₅ , 3.19 g of an orange solid were obtained (yield 93%).
[500] ¹ H-NMR analysis (DMSO-d ₆ , 200 MHz, ppm) according to the desired product was as follows:
[501] 7.80 (m, 2 H); 6.58 (m, 1 H); 4.91 (d, J = 3.3 Hz, 1 H); 4.25 (m, 1 H), 3.60 (m, 2 H); 3.41 (m, 1 H); 3.18 ppm (m, 1 H); 2.34 (s, 3 H); 1.82 (m, 2 H)
[502] Elemental analysis was as follows:
[503] %CHNO Theory59.456.3512.6021.60 Found58.916.4012.2021.42
[504] Step 2: Preparation of 1- (4-amino-2-methylphenyl) pyrrolidine-3-ol hydrochloride
[505] 1- (4-nitro-2-methylphenyl) pyrrolidin-3-ol (2 g, 9.00 mmol) obtained in the previous step was dissolved in 40 ml of anhydrous ethanol in the presence of 1 g of wet activated carbon-phase-palladium and Suspended in 8 ml of cyclohexene. Argon was then bubbled into the reaction medium for several minutes and then refluxed for 4 hours. The reaction mixture was filtered into a vacuum flask cooled to −5 ° C. containing 100 ml of diisopropyl ether, 50 ml of isopropanol and 4 equivalents of hydrochloric ethanol (6.2 ml). The precipitate obtained was quickly filtered and dried in a vacuum oven at 30 ° C. 1.20 g of pale pink solid were obtained with a yield of 58%.
[506] ¹ H-NMR analysis (MeOH-d ₄ , 200 MHz, ppm) according to the desired product was as follows:
[507] 7.79 (d, J = 9 Hz, 1 H); 7.28 (m, 2 H); 4.58 (m, 1 H): 3.94 (m, 2 H); 3.53 (m, 1 H); 3.13 (m, 1 H); 2.48 (s, 3 H); 2.20 (m, 2 H).
[508] Elemental analysis was as follows:
[509] %CHNOCl Theory46.807.099.9311.3424.82 Found46.587.319.3911.2623.34
[510] The product obtained contains 2 moles of HCl and 1 mole of water.
[511] Example 9: Synthesis of 1- (4-amino-3-methylphenyl) -pyrrolidin-3-ol hydrochloride
[512]
[513] Step 1: Preparation of 1- (4-nitro-3-methylphenyl) pyrrolidin-3-ol
[514] 1.90 ml of 1-fluoro-3-methyl-4-nitrobenzene (0.0155 mol), 1.3 g of sodium bicarbonate (0.0155 mol) and 15 ml of dioxane / water (8/2) mixture were added to a three neck flask. Put in. 1.35 g of racemic 3-pyrrolidinol (0.0155 mol) was quickly added to this mixture. The heterogeneous mixture was refluxed (87 ° C.) for 24 hours. The reaction mixture was then poured into ice cold water; A yellow precipitate was obtained, which was filtered and rinsed with water. After drying in vacuo in the presence of P ₂ O ₅ , 2.7 g of a yellow solid were obtained (yield 78%).
[515] ¹ H-NMR analysis (DMSO-d ₆ , 200 MHz, ppm) according to the desired product is as follows:
[516] 8.03 (d, J = 9 Hz, 1H); 6.52 (m, 2 H); 5.08 (d, J = 3.2, 1 H); 4.44 (m, 1 H); 3.50 (m, 3 H); 3.25 (m, 1 H); 2.58 (s, 3 H); 2.05 (m, 2 H).
[517] Elemental analysis values are as follows:
[518] %CHNO Theory59.456.3512.6021.60 Found58.826.4812.1621.50
[519] Step 2: Preparation of 1- (4-amino-3-methylphenyl) pyrrolidine-3-ol hydrochloride
[520] 1- (4-nitro-3-methylphenyl) pyrrolidin-3-ol (2 g, 9.00 mmol) obtained in the previous step was dissolved in 40 ml of anhydrous ethanol in the presence of 1 g of wet activated carbon-phase-palladium and Suspended in 8 ml of cyclohexene. Argon was then bubbled into the reaction medium for several minutes and then refluxed for 4 hours. The reaction mixture was filtered into a vacuum flask cooled to −5 ° C. containing 100 ml of diisopropyl ether, 50 ml of isopropanol and 4 equivalents of hydrochloric ethanol (6.2 ml). The precipitate obtained was quickly filtered and dried in a vacuum oven at 30 ° C. 1.93 g of pale pink solid were obtained in 94% yield.
[521] ¹ H-NMR analysis (MeOH-d ₄ , 200 MHz, ppm) according to the desired product is as follows:
[522] 7.44 (m, 1 H); 7.33 (m, 2 H); 4.66 (m, 1 H): 3.79 (m, 3 H); 3.52 (m, 1 H); 2.45 (s, 3 H); 2.37 (m, 2 H).
[523] Elemental analysis values are as follows:
[524] %CHNOCl Theory46.807.099.9311.3624.82 Found47.496.959.6611.3224.56
[525] The product obtained contains 2 moles of HCl and 1 mole of water.
[526] Dyeing Example
[527] The following dye compositions according to the invention were prepared:
[528] ExampleOne23(4-amino-3-methylphenyl) pyrrolidin-3-ylamine, dihydrochloride3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3Resorcinol3 × 10 ^-3 -- 1-β-hydroxyethyloxy-2,4-diaminobenzene-3 × 10 ^-3 - 1-methyl-4-aminophenol- 3 × 10 ^-3Conventional dye supports(*)(*)(*) Demineralized qs100 g100 g100 g Example4567 1- (4-amino-3-methoxyphenyl) pyrrolidin-3-ol, dihydrochloride3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3Resorcinol3 × 10 ^-3 --- 1-β-hydroxyethyloxy-2,4-diaminobenzene-3 × 10 ^-3 -- 1-methyl-4-aminophenol--3 × 10 ^-3 - Conventional dye supports(*)(*)(*)(*) Demineralized qs100 g100 g100 g100 g
[529] Example8910(R) -1- (4-aminophenyl) pyrrolidin-3-ol, dihydrochloride3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3Resorcinol3 × 10 ^-3 1-β-hydroxyethyloxy-2,4-diaminobenzene 3 × 10 ^-3 1-methyl-4-aminophenol 3 × 10 ^-3Conventional dye supports(*)(*)(*) Demineralized qs100 g100 g100 g Example1112N- [1- (4-aminophenol) pyrrolidin-3-yl] acetamide dihydrochloride3 × 10 ^-3 3 × 10 ^-3Resorcinol3 × 10 ^-3 1-β-hydroxyethyloxy-2,4-diaminobenzene 3 × 10 ^-3Conventional dye supports(*)(*) Demineralized qs100 g100 g Example13141516 [1- (4-aminophenyl) pyrrolidin-3-yl] dimethylamine dihydrochloride3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3Resorcinol3 × 10 ^-3 --- 1-β-hydroxyethyloxy-2,4-diaminobenzene-3 × 10 ^-3 -- 1-methyl-4-aminophenol--3 × 10 ^-3 - Conventional dye supports(*)(*)(*)(*) Demineralized qs100 g100 g100 g100 g Example17181920 1- (4-aminophenyl) pyrrolidin-3-ylamine dihydrochloride3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3Resorcinol3 × 10 ^-3 --- 1-β-hydroxyethyloxy-2,4-diaminobenzene-3 × 10 ^-3 -- 1-methyl-4-aminophenol--3 × 10 ^-3 - Conventional dye supports(*)(*)(*)(*) Demineralized qs100 g100 g100 g100 g Example21222324 1- (4-aminophenyl) pyrrolidin-3-ol, dihydrochloride,3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3 3 × 10 ^-3Resorcinol3 × 10 ^-3 --- 1-β-hydroxyethyloxy-2,4-diaminobenzene-3 × 10 ^-3 -- 1-methyl-4-aminophenol--3 × 10 ^-3 - Conventional dye supports(*)(*)(*)(*) Demineralized qs100 g100 g100 g100 g
[530] (*) Conventional dye supports
[531] 4.0 g of oleyl alcohol polyglycerolized with 2 moles of glycerol
[532] 5.69 g A.M. oleyl alcohol, polyglycerolated with 4 moles of glycerol, containing 78% active substance (A.M.).
[533] 3.0 g of oleic acid
[534] -Tradename Ethomeen O12 by Akzo 7.0 g of oleylamine, containing 2 moles of ethylene oxide, sold as
[535] 3.0 g A.M sodium salt with diethylaminopropyl laurylaminosuccinamate, 55% A.Mbar.
[536] -5.0 g oleyl alcohol
[537] 12.0 g oleic acid diethanolamide
[538] -3.5 g propylene glycol
[539] 7.0 g of ethyl alcohol
[540] -0.5 g of dipropylene glycol
[541] 9.0 g of propylene glycol monomethyl ether
[542] 0.455 g A.M. sodium metabisulfite as an aqueous solution containing 35% A.M.
[543] 0.8 g ammonium acetate
[544] Antioxidants, sequestering agents qs
[545] -Spices, preservatives qs
[546] 10.2 g of aqueous ammonia containing 20% NH ₃
[547] In use, each dye composition was mixed with an equivalent amount of oxidizing composition having a pH of about 3, consisting of 20-volume aqueous hydrogen peroxide solution (6 wt%).
[548] Each mixture obtained has a pH of about 9.5. Each mixture is applied to a skein of natural gray hair containing 90% white hair. After placing the mixture on the skein for 30 minutes, the skein of hair is rinsed, washed with standard shampoo, rinsed and dried.
[549] Skein of color, Minolata CM 2002 Evaluation was made on L * a * b * systems using a photometer (Illuminant D65).
[550] In the L * a * b * system, the three parameters represent intensity (L *), red-green color component (a *) and yellow-blue color component (b *), respectively. According to this system, the higher the L value, the more pale or less dense the color. Conversely, the smaller the L value, the darker or darker the color.
[551] ExampleNatural white hairL *a *b * One35.23.86.1 223.8-1.9-8.3 325.44.8-10.45 433.50.4-4.9 526.2-3.3-11.5 629.5-0.5-13.3 748.22.66.8 828.24.00.3 922.22.1-13.3 1020.13.5-8.0 1131.33.91.2 1223.20.06-13.05 1337.355.45.6 1426.00.01-11.8 1534.68.0-6.3 1649.22.58.75 1729.95.453.4 1822.12.22-12.8 1924.18.1-9.7 2040.93.36.7 2129.94.440.58 2223.60.7-13.8 2322.95.8-14.2 2447.61.08.45
[552] The following dye compositions according to the invention were prepared:
[553] Example252627282930 N- (4-aminophenyl) -3-hydroxypyrrolidine, dihydrochloride (compound of formula I)3 x 10 ^-3 moles3 x 10 ^-3 moles---- N- (4-amino-2-methylphenyl) -3-hydroxypyrrolidine, dihydrochloride (compound of formula I)--3 x 10 ^-3 moles3 x 10 ^-3 moles-- N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine, dihydrochloride (compound of formula I)----3 x 10 ^-3 moles3 x 10 ^-3 moles 2,4-Diimino-1- (β-hydroxyethyloxy) benzene, dihydrochloride (coupling agent)3 x 10 ^-3 moles-3 x 10 ^-3 moles-3 x 10 ^-3 moles- 1,3-dihydroxybenzene (coupling agent)-3 x 10 ^-3 moles-3 x 10 ^-3 moles-3 x 10 ^-3 moles Conventional dye supports(*)(*)(*)(*)(*)(*) Demineralized qs100 g100 g100 g100 g100 g100 g
[554] (*) Conventional dye support: same as described above
[555] In use, each dye composition was mixed with an equivalent amount of oxidizing composition having a pH of about 3, consisting of 20-volume aqueous hydrogen peroxide solution (6 wt%).
[556] Each mixture obtained has a pH of about 9.5 and each mixture is applied to a skein of natural gray hair comprising 90% of white hair. After 30 minutes, the skein of hair is rinsed off, washed with standard shampoo and dried.
[557] Skein of hair was dyed in the shades shown in the table below:
[558] ExampleNatural Hair Top Colors 25blue 26Ashen Violet Pearly Blonde 27Grayish light blue 28Very pale golden grayish beige 29Pale matte blue 30Pale golden grayish gray

权利要求:
Claims (21)
[1" claim-type="Currently amended] A composition for oxidative dyeing of keratin fibers, in particular human keratin fibers, such as hair, comprising at least one selected from para-phenylenediamine derivatives comprising a pyrrolidinyl group of the formula (I) and acid addition salts thereof in a medium suitable for dyeing: A composition comprising an oxidizing base:
[Formula I]
[In meals:
R ₁ is a hydrogen atom; Halogen atoms selected from chlorine and bromine atoms; May comprise one or more double bonds and / or one or more triple bonds (the double bond may optionally be an aromatic group), and one or more carbon atoms may be replaced with oxygen, nitrogen or sulfur atoms or SO ₂ groups, Independently of each other, it represents a linear or branched C ₁ -C ₇ alkyl radical which may be substituted with one or more halogen atoms (branch (s) may form one or more 3- to 6-membered carbon-based rings); The radical R ₁ does not comprise a peroxide bond or a diazo, nitro or nitroso radical;
R ₂ is a hydroxyl radical; Amino radicals; One or more hydroxyl or linear or branched C ₁ -C ₄ alkyl radicals wherein R ₃ is substituted with one or more radicals selected from the group consisting of halogen atoms, C ₁ -C ₂ alkoxy, amino or C ₁ -C ₂ aminoalkyl An -OR ₃ group representing a C ₃ -C ₄ alkyl radical substituted with a radical; Methylcarbonyl radicals; R ₄ and R ₅ are, independently of each other, substituted with one or more radicals selected from the group consisting of hydrogen atom, halogen atom and hydroxyl, C ₁ -C ₂ alkoxy, amino or C ₁ -C ₂ aminoalkyl radical Or a —NR ₄ R ₅ group representing a branched C ₁ -C ₄ alkyl radical.
[2" claim-type="Currently amended] The compound of claim 1, wherein in formula (I), R ₁ represents a hydrogen atom or methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl, To represent a 2-hydroxyethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or 3-hydroxyethyloxy radicals Characterized by a composition.
[3" claim-type="Currently amended] 3. A compound according to claim 2, wherein in formula (I) R ₁ represents a hydrogen atom or a methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy or 2-hydroxyethoxy radical Characterized by a composition.
[4" claim-type="Currently amended] The compound of claim 1, wherein in formula (I), R ₂ is a hydroxyl radical; Amino radicals; R ₃ is halogen atom, C ₁ -C ₂ alkoxy, amino and C ₁ -C ₂ -OR ₃ represents a linear or branched C ₁ -C ₄ alkyl radical substituted by one or more radicals selected from the group consisting of amino alkyl group; Methylcarbonyl radicals; R ₄ and R ₅ are, independently of each other, substituted with one or more radicals selected from the group consisting of hydrogen atom, halogen atom and hydroxyl, C ₁ -C ₂ alkoxy, amino or C ₁ -C ₂ aminoalkyl radical Or a -NR ₄ R ₅ group representing a branched C ₁ -C ₄ alkyl radical.
[5" claim-type="Currently amended] The composition of claim 4 wherein R ₂ represents a hydroxyl, acetoxy, amino, methylamino, dimethylamino or 2-hydroxyethylamino radical.
[6" claim-type="Currently amended] The para-phenylenediamine according to any one of claims 1 to 5, wherein the para-phenylenediamine comprising a pyrrolidinyl group of formula I is N- (4-aminophenyl) -3-hydroxypyrrolidine, N- (4). -Amino-2-methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-methoxyphenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (2-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1-hydroxy Ethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1,2-dihydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino- 3-methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methoxyphenyl) -3- Hydroxypyrrolidine, N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1-hydroxyethyl) phenyl ) -3-hydroxypyrrolidine, N- (4-amino-3- (1,2-dihydroxyethyl) phenyl) -3-hydroxypyri Lolidine, N- (4-aminophenyl) -3-aminopyrrolidine, N- (4-amino-2-methylphenyl) -3-aminopyrrolidine, N- (4-amino-2-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-2-methoxyphenyl) -3-aminopyrrolidine, N- (4-amino-2- (2-hydroxyethyl) phenyl) -3- Aminopyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-2- (1,2-dihydroxyethyl) Phenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methylphenyl) -3-aminopyrrolidine, N- (4-amino-3-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-3-methoxyphenyl) -3-aminopyrrolidine, N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- ( 4-amino-3- (1-hydroxyethyl) phenyl) -3-aminopyrrolidine and N- (4-amino-3- (1,2-dihydroxyethyl) phenyl) -3-aminopyrroli Dean, and acid addition salts thereof.
[7" claim-type="Currently amended] The para-phenylenediamine derivative (s) and / or acid addition salts thereof according to any one of claims 1 to 6, wherein the para-phenylenediamine derivative (s) comprising a pyrrolidinyl group of formula (I) is from 0.0005% by weight to the total weight of the dye composition. 12% by weight, preferably 0.005% to 6% by weight.
[8" claim-type="Currently amended] 8. Composition according to any one of the preceding claims containing at least one coupling agent selected from meta-phenylenediamine, meta-aminophenol, meta-diphenol and heterocyclic coupling agents. .
[9" claim-type="Currently amended] 9. The compound of claim 1, wherein the additional coupling agent is a heterocyclic coupling agent, substituted meta-diphenol, substituted meta-phenylenediamine, naphthol, acylated naphthol and A composition characterized in that it is selected from meta-aminophenols:
[Formula III]
[In meals:
R ₅ represents a hydrogen atom or a C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl radical,
R ₆ represents a hydrogen atom, a C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy radical or a halogen atom selected from chlorine, bromine and fluorine,
R ₇ is a hydrogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, C ₁ -C ₄ monohydroxy Alkoxy or a C ₂ -C ₄ polyhydroxyalkoxy radical.
[10" claim-type="Currently amended] The method of claim 8, wherein the coupling agent is 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 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, sesa Molar, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindolin, 2,6-dihydroxy -4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo [ 3,2-c] -1,2,4-triazole and 2,6-dimethylpyrazolo [1,5-b] -1,2,4-triazole, and acid addition salts thereof Characterized in that the composition.
[11" claim-type="Currently amended] The composition according to claim 8, wherein the coupling agent (s) represents 0.0001% to 10% by weight relative to the total weight of the dye composition.
[12" claim-type="Currently amended] 12. The composition of claim 11, wherein the coupling agent (s) represents 0.005% to 5% by weight relative to the total weight of the dye composition.
[13" claim-type="Currently amended] 13. Para-phenylenediamine, bis (phenyl) alkylenediamine, other than a compound of formula (I) as defined in any one of claims 1 to 5, A composition characterized in that it contains at least one further oxidation base selected from para-aminophenol, ortho-aminophenol and heterocyclic bases and acid addition salts thereof.
[14" claim-type="Currently amended] The method of claim 13, wherein the additional base is selected from heterocyclic oxidation bases, double bases, substituted para-aminophenols, ortho-aminophenols, para-phenylenediamine derivatives of formula II and acid addition salts thereof. A composition comprising:
[Formula II]
[In meals:
-R ₅ is a hydrogen atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) an alkyl radical, a C ₁ -C ₄ alkyl radical substituted with one or more nitrogenous groups, a phenyl radical, or a 4′-aminophenyl radical;
R ₆ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl radicals, or C ₁ -C ₄ alkyl radicals substituted with one or more nitrogenous groups;
R ₇ is a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine atom, a C ₁ -C ₄ alkyl radical, a C ₁ -C ₄ monohydroxyalkyl radical, a C ₁ -C ₄ hydroxyalkoxy radical, acetyl Amino (C ₁ -C ₄ ) alkoxy radicals, C ₁ -C ₄ mesylaminoalkoxy radicals, or carbamoylamino (C ₁ -C ₄ ) alkoxy radicals,
R ₈ represents hydrogen or a halogen atom or a C ₁ -C ₄ alkyl radical.
[15" claim-type="Currently amended] The composition according to claim 13, wherein the additional oxidation base (s) represent 0.0005% to 12% by weight relative to the total weight of the dye composition.
[16" claim-type="Currently amended] The composition according to claim 1, wherein the acid addition salt is selected from hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, phosphate and acetate. .
[17" claim-type="Currently amended] 17. A composition according to any one of the preceding claims containing at least one polymer selected from:
(i) amphoteric polymers,
(ii) a cationic polymer comprising repeat units of formula (II) or (III), and
(iii) a polymer other than above which is amphiphilic and comprises at least one hydrocarbon chain,
Structural Formula (II):

[In meals:
R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and represent an aliphatic, cycloaliphatic or arylaliphatic radical or lower hydroxyalkylaliphatic radical comprising 1 to 20 carbon atoms, or R ₅ , R ₆ , R ₇ and R ₈ together or separately together, together with the nitrogen atom to which they are attached, constitute a heterocycle optionally containing a second hetero atom other than nitrogen, or R ₅ , R ₆ , R ₇ and R ₈ are linear or branched, substituted with a -CO-OR ₁₃ -D or -CO-NH-R ₁₃ -D group wherein nitrile, ester, acyl, amide or R ₁₃ is alkylene and D is a quaternary ammonium group A C ₁ -C ₆ alkyl radical;
A ₁ and B ₁ may be linear or branched, saturated or unsaturated, and at least one aromatic ring connected or inserted into the main chain, or at least one oxygen or sulfur atom, or sulfoxide, sulfone, disulfide, amino, alkylamino A polymethylene group containing 2 to 20 carbon atoms which may contain hydroxyl, quaternary ammonium, ureido, amide or ester groups;
A ₁ , R ₅ and R ₇ may form a piperazine ring with the two nitrogen atoms to which they are attached; Further, if A ₁ represents a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, then B ₁ also n is from 1 to 100, preferably from 1 to 50, and T represents CH ₂ ) _n -CO-T-OC- (CH ₂ ) _n -can be represented:
a) a glycol moiety of the formula: -O-Z-O-, wherein Z represents a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulas:
-(CH ₂ -CH ₂ -O) _x -CH ₂ -CH _2-
-[CH ₂ -CH (CH ₃ ) -O] _y -CH ₂ -CH (CH ₃ )-
(Wherein x and y represent an integer from 1 to 4 representing a limited and unique degree of polymerization, or any number from 1 to 4 representing an average degree of polymerization);
b) bis-secondary diamine residues such as piperazine derivatives;
c) Y is a linear or branched hydrocarbon-based radical, or alternatively a divalent radical:
-CH ₂ -CH ₂ -SS-CH ₂ -CH _2-
A bis-primary diamine residue of the formula -NH-Y-NH-;
d) ureylene groups of the formula -NH-CO-NH-;
X ₁ ⁻ is an anion derived from mineral or organic acids and preferably chlorine or bromine];
Structural formula (III)

[In meals:
R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and represent a hydrogen atom or methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or —CH ₂ CH ₂ (OCH ₂ CH ₂ ) represents a _p OH radical (wherein p is equal to 0 or an integer from 1 to 6),
Provided that R ₉ , R ₁₀ , R ₁₁ and R ₁₂ do not represent a hydrogen atom at the same time,
R and s, which may be the same or different, are an integer from 1 to 6,
D is 0 or represents a-(CH ₂ ) _q -CO- group (q is equal to 0 or an integer from 1 to 34),
A represents a dihalide radical, or preferably, -CH ₂ -CH ₂ -O-CH ₂ -CH _2- ,
X ₂ ⁻ represents an anion derived from a mineral or organic acid, preferably a halogen atom.
[18" claim-type="Currently amended] A method of oxidative dyeing of keratin fibers, wherein at least one dye composition as defined in any one of claims 1 to 17 is applied to the fiber and added to the dye composition when used, or applied simultaneously or continuously. Wherein the color appears at an acidic, neutral or alkaline pH with the aid of an oxidant present in the composition.
[19" claim-type="Currently amended] 19. The method of claim 18, wherein the oxidant present in the oxidizing composition is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, perchlorates, peracids, and enzymes.
[20" claim-type="Currently amended] A multicompartment apparatus or multicompartment dye kit, wherein the first compartment comprises the dye composition as defined in claim 1 and the second compartment comprises an oxidizing composition.
[21" claim-type="Currently amended] Colored, resulting from the oxidation of at least one compound of formula (I) as defined in any one of claims 1 to 5, in the presence of at least one oxidant and optionally at least one coupling agent and / or at least one further oxidation base. product.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-03-14|Priority to FR0003250A

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2000-03-14|Priority to FR00/03250

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2001-03-13|Application filed by 조지안느 플로, 로레알

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2001-03-13|Priority to PCT/FR2001/000745

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2001-12-28|Publication of KR20010113945A

优先权:

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申请号 | 申请日 | 专利标题

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FR0003250A|FR2806299B1|2000-03-14|2000-03-14|Compositions for dyeing keratinic fibers containing pyrrolidinyl grouped paraphenylenediamine derivatives|

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FR00/03250|2000-03-14|

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PCT/FR2001/000745|WO2001068043A2|2000-03-14|2001-03-13|Dyeing compositions for keratinous fibres containing paraphenylenediamine derivatives with pyrrolidinyl group|