USE FOR DYEING KERATIN FIBRES OF A COMPOUND OF AZOMETHINE TYPE BEARING A PYRAZOLOPYRIDINE UNIT

Abstract

The invention relates to a compound chosen from dyes of azomethine type bearing a pyrazolopyridine unit of formula (I) and the leuco forms thereof of formula (II) below, and also the optical isomers and geometrical isomers thereof, the tautomers thereof, the addition salts thereof with an acid or a base, and the solvates thereof. The invention also relates to the use of these particular compounds for dyeing keratin fibres.

##STR00001##

Claims

1. Compound chosen from dyes of azomethine type bearing a pyrazolopyridine unit of formula (I) and the leuco forms thereof of formula (II) below, and also the optical isomers and geometrical isomers thereof, the tautomers thereof, the addition salts thereof with an acid or a base, and the solvates thereof such as hydrates: ##STR00036## in which formulae (I) and (II): Z.sub.1 represents an oxygen atom or a group —NR.sub.6—; when Z.sub.1 represents —NR.sub.6—, then R.sub.1 and R.sub.6 may form, together with the nitrogen atom to which they are attached, an optionally substituted, 5- to 8-membered, saturated, unsaturated or aromatic heterocycle; R.sub.1 and R.sub.6 each independently represent: a hydrogen atom; a C.sub.1-C.sub.10 alkyl radical optionally interrupted with one or more non-adjacent heteroatoms, preferably oxygen, and/or optionally substituted, preferably with one or more groups chosen from i) hydroxyl, ii) optionally substituted 5- to 8-membered, saturated, unsaturated or aromatic (hetero)cycle, iii) —N(R′)R″, iv) —N.sup.+R′R″R′″ with R′, R″ and R′″ each independently representing a C.sub.1-C.sub.6 alkyl group; an optionally substituted, saturated, unsaturated or aromatic 5- to 8-membered (hetero)cycle; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 each independently represent: a hydrogen atom; an optionally substituted C.sub.1-C.sub.4 alkyl radical; a group chosen from —NH.sub.2, —N(H)R.sub.10, —N(R.sub.11)—R.sub.12, —OH and —OR.sub.9, with R.sub.9 and R.sub.10 representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, R.sub.11 and R.sub.12, which may be identical or different, representing an optionally substituted, linear or branched C.sub.1-C.sub.6 alkyl, it being possible for R.sub.11 and R.sub.12 to form, together with the nitrogen atom to which they are attached, a saturated, unsaturated or aromatic 5- to 8-membered heterocycle optionally containing one or more other heteroatoms or groups chosen from oxygen and nitrogen, the heterocycle being optionally substituted; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 may form, in pairs, with adjacent radicals, an optionally substituted, saturated or unsaturated or aromatic (hetero)cycle; R′.sub.2 and R′.sub.3, which may be identical or different, represent: a hydrogen atom; a C.sub.1-C.sub.6 and preferably C.sub.1-C.sub.4 alkyl radical, optionally substituted with one or more hydroxyl radicals; a C.sub.1-C.sub.6 alkyl carboxylate radical; a carboxyl radical; R′ represents: a hydrogen atom; a C.sub.1-C.sub.6 alkyl radical; R′.sub.6 represents: a hydrogen atom; a halogen atom; a linear or branched C.sub.1-C.sub.10 alkyl radical, optionally interrupted with one or more non-adjacent oxygen atoms and/or one or more non-adjacent divalent groups —N(R′.sub.9)— and optionally substituted with one or more radicals, which may be identical or different, chosen from —OH and —N(R′.sub.7)R′.sub.8; a carboxyl radical; a C.sub.1-C.sub.10 alkyl carboxylate; a radical CONR′.sub.7R′.sub.8; a C.sub.1-C.sub.10 alkoxy radical or a C.sub.1-C.sub.10 (poly)hydroxyalkoxy radical; a (poly)(C.sub.1-C.sub.10 alkoxy)-(C.sub.1-C.sub.10 alkoxy) radical; a radical —O-Ak-N(R′.sub.9)R′.sub.10 in which Ak is a linear C.sub.1-C.sub.8 or branched C.sub.3-C.sub.8 divalent alkylene radical, optionally interrupted with one or more oxygen atoms and/or non-adjacent divalent groups —N(R′.sub.7)—; R′.sub.7 and R′.sub.8, which may be identical or different, represent: a hydrogen atom; a C.sub.1-C.sub.8 alkyl radical optionally substituted with one or more hydroxyl radicals; R′.sub.9 and R′.sub.10, which may be identical or different, represent i) a linear or branched C.sub.1-C.sub.6 alkyl radical, ii) a C.sub.2-C.sub.6 alkenyl radical or iii) a C.sub.2-C.sub.6 alkynyl radical; R′.sub.9 and R′.sub.10 may form, with the nitrogen that bears them, a saturated or unsaturated 5- to 8-membered heterocycle, one of the chain members possibly being an oxygen atom or a nitrogen atom, or a divalent radical —N(R′.sub.11)— with R′.sub.11 representing a hydrogen atom or a C.sub.1-C.sub.4 alkyl group, optionally substituted with one or more radicals chosen from —OH, —N(R′.sub.7)R′.sub.8 and C.sub.1-C.sub.4 alkyl; R″ represents: a hydrogen atom; a linear or branched C.sub.1-C.sub.10 alkyl radical, optionally interrupted with an oxygen atom or a divalent group —N(R)— with R representing a hydrogen atom or a C.sub.1-C.sub.4 alkyl group; it being understood that when the compound of formula (I) or (II) is positively charged, then it comprises as many anionic counterions as cationic charges to achieve the electrical neutrality of the molecule.

2. Compound according to claim 1, characterized in that Z.sub.1 represents an oxygen atom or an —N(H)— radical.

3. Compound according to claim 1 or 2, characterized in that R.sub.1 represents a C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 alkyl radical substituted with a hydroxyl group, a C.sub.1-C.sub.6 alkyl radical substituted with a (di)(C.sub.1-C.sub.4 alkyl)amino such as dimethylamino, a C.sub.1-C.sub.6 alkyl radical substituted with a nitrogenous heterocycle chosen from imidazolyl, pyrrolidinyl, piperidyl, morpholinyl and piperazinyl.

4. Compound according to any one of the preceding claims, characterized in that R.sub.2, R.sub.3, R.sub.4 and R.sub.5 independently represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical.

5. Compound according to any one of the preceding claims, characterized in that R′.sub.2 and R′.sub.3 independently represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical optionally substituted with one or more hydroxyl radicals.

6. Compound according to any one of the preceding claims, characterized in that R′ represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical.

7. Compound according to any one of the preceding claims, characterized in that R′.sub.6 represents i) a hydrogen atom; ii) a linear or branched C.sub.1-C.sub.6 alkyl radical, optionally substituted with a hydroxyl radical; iii) a C.sub.1-C.sub.6 hydroxyalkoxy radical; iv) a radical —O-Ak-NR′.sub.9R′.sub.10 in which Ak denotes a linear divalent C.sub.1-C.sub.8 alkylene radical with: R′.sub.9 and R′.sub.10 independently denoting a saturated, linear or branched C.sub.1-C.sub.4 alkyl radical; or alternatively R′.sub.9 and R′.sub.10 form, together with the nitrogen atom that bears them, a heterocycle chosen from pyrrolidinyl, morpholinyl, imidazolyl, piperazinyl and piperidyl, said heterocycle being optionally substituted with one or more radicals chosen from —OH and C.sub.1-C.sub.4 alkyl.

8. Compound according to any one of the preceding claims, characterized in that R″ represents a hydrogen atom or a linear C.sub.1-C.sub.6 alkyl radical.

9. Compound according to any one of the preceding claims, characterized in that it is chosen from the compounds of formulae (I) and (II), and also the optical isomer, geometrical isomer and tautomer forms thereof, the addition salts thereof with an acid or a base, and the solvates thereof such as hydrates: ##STR00037## in which formulae (I) and (II): R.sub.1═—CH.sub.2CH.sub.2OH, —CH.sub.2CH.sub.2N(CH.sub.3).sub.2, —CH.sub.2CH.sub.2CH.sub.2N(CH.sub.3).sub.2 when Z.sub.1═O, R.sub.1═—CH.sub.2CH.sub.2N(CH.sub.3).sub.2, —CH.sub.2CH.sub.2CH.sub.2N(CH.sub.3).sub.2 when Z.sub.1═—N(R.sub.6)— and R.sub.6 represents a hydrogen atom, R′, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 denote a hydrogen atom, R′.sub.2, R′.sub.3 and R″, which may be identical or different, denote a hydrogen atom or a methyl radical, and R′.sub.6 denotes a hydrogen atom or a methyl, ethyl, —O—(CH.sub.2).sub.2—OH, —O—(CH.sub.2).sub.3—OH, —O—(CH.sub.2).sub.2-Het or —O—(CH.sub.2).sub.3-Het radical with Het representing a pyrrolidinyl or morpholino or imidazolyl or N-methylpiperazino or piperidino group.

10. Composition for dyeing keratin fibres comprising, in a medium that is suitable for dyeing, one or more compounds as defined in any one of claims 1 to 9.

11. Composition according to claim 10, characterized in that the compound(s) as defined in any one of claims 1 to 9 are present in an amount ranging from 0.01% to 15% by weight and preferably from 0.05% to 10% by weight relative to the total weight of the composition.

12. Composition according to claim 10 or 11, characterized in that it also comprises one or more oxidizing agents.

13. Use of one or more compounds as defined in any one of claims 1 to 9, for dyeing keratin fibres.

14. Process for dyeing keratin fibres, characterized in that at least one dye composition according to any one of claims 10 to 12 is applied to these fibres.

15. Process for preparing compounds of formulae (I) and (II) as defined in any one of claims 1 to 9, according to the following scheme: ##STR00038## which consists: in a first stage, in reacting a pyrazolo[1,5-a]pyridine compound A1 comprising an amino group in position 3 with an indole compound A2 which is free in position 5 and comprising in position 4 an amino group, preferably, this reaction is performed i) in a polar protic solvent such as in water or a mixture of water/C.sub.1-C.sub.10 alcohol such as ethanol, ii) and/or in the presence of one or more basifying agents, as defined below, chosen in particular from sodium hydroxide, potassium hydroxide, a mineral carbonate such as potassium carbonate, or an acetate, iii) and/or in the presence of a chemical oxidizing agent such as peroxides or persulfates, iv) and/or at a temperature between room temperature, i.e. 25° C., and the reflux temperature of the solvent, preferably at room temperature, and then in a second stage, in maintaining the reaction medium under stirring for a time of between 5 minutes and 48 hours, more particularly between 30 minutes and 24 hours if the reaction is performed at room temperature; and then the reaction product (I) is optionally purified via a standard technique such as recrystallization, filtration or chromatography; according to one variant, compound (I), once purified, is reduced using a reducing agent such as catalytic reduction with hydrogen borne on graphite, or using transition metals such as palladium or nickel, or alternatively by reduction with hydrides or borohydrides, or with thioglycolic acid derivatives, to give the leuco compound (II); optionally followed by a step of purification via a standard technique as mentioned previously to give the leuco compound (II); according to another variant, compound (I) is not purified, and is reduced using a reducing agent as mentioned previously to give the leuco compound (II), optionally followed by a step of purification via a standard technique as mentioned previously.

Description

EXAMPLES

Example 1: Synthesis of 2-[(3-{[4-imino-2,3,7-trimethyl-1,4-dihydro-5H-indol-5-ylidene]amino}pyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride

[0183] ##STR00032##

[0184] 39.60 g (172.17 mmol) of 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride are placed in a 2-litre one-necked round-bottomed flask equipped with a bubbler, and are dissolved in a mixture consisting of 80 ml of ethanol and 80 ml of water.

[0185] 30 g (172.17 mmol) of 2,3,7-trimethyl-1H-indol-4-amine, 80 ml (860.85 mmol) of ammonia at 20% in water and 93 ml (860.85 mmol) of hydrogen peroxide at 30% in water are added to this solution.

[0186] The solution is then stirred at room temperature for 24 hours. The dark brown precipitate formed is isolated by filtration, washed with water and then dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight.

[0187] A product in the form of a dark brown powder is obtained.

[0188] The spectrometric analyses show that 2-[(3-{[4-imino-2,3,7-trimethyl-1,4-dihydro-5H-indol-5-ylidene]amino}pyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride is obtained.

Example 2: Synthesis of 2-[(3-{[4-imino-7-methyl-1,4-dihydro-5H-indol-5-ylidene]amino}pyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol

[0189] ##STR00033##

[0190] A mixture of 30 ml of water and 10 ml of ethanol is placed in a 250 ml one-necked round-bottomed flask equipped with a bubbler, followed by addition of 87.18 mg of 2-[(3-aminopyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol hydrochloride and 55.5 mg of 7-methyl-1H-indol-4-amine.

[0191] 4 ml of ammonia at 20% in water and 4 ml of 20-volumes aqueous hydrogen peroxide solution are added to this solution.

[0192] The solution is then stirred at room temperature for 24 hours. The dark precipitate formed is isolated by filtration, washed with water and then dried in a desiccator under vacuum at 30° C. in the presence of a desiccant, to constant weight.

[0193] A product in the form of a black powder is obtained.

[0194] The spectrometric analyses show that 2-[(3-{[4-imino-7-methyl-1,4-dihydro-5H-indol-5-ylidene]amino}pyrazolo[1,5-a]pyridin-2-yl)oxy]ethanol is obtained.

Example 3: Examples of Dyeing at Neutral pH

[0195] The following dye compositions were prepared using the ingredients indicated in the table below, and especially the dyes synthesized in Examples 1 and 2 above.

TABLE-US-00001 Dye 1 or 2 .sup.(1) 10.sup.−3 mol pH 7 dye support .sup.(2) Demineralized water qs 100 g .sup.(1) Dye synthesized in Example 1 or 2 above: Dye 1 (synthesized in Example 1) [00034] Dye 2 (synthesized in Example 2) [00035] .sup.(2) pH 7 dye support 96° ethyl alcohol 20.8 g Pentasodium salt of diethylenetriaminepentaacetic 0.48 g AM* acid as an aqueous solution at 40% by weight (C.sub.8-C.sub.10alkyl) polyglucoside as an aqueous solution  3.6 g AM* at 60% by weight Benzyl alcohol  2.0 g Polyethylene glycol containing 8 units of ethylene  3.0 g oxide Na.sub.2HPO.sub.4 0.28 g KH.sub.2PO.sub.4 0.46 g *AM: Active Material

[0196] Each composition was applied to locks of grey hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

[0197] The shades obtained are given in the table below:

TABLE-US-00002 Dye 1 2 Shade observed Brown Dark brown

[0198] For the colourings in the presence of an oxidizing agent: at the time of use, each of the compositions described above was mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight relative to the total weight of 100 grams). A final pH of 7 is obtained.

[0199] The shades obtained are given in the table below:

TABLE-US-00003 Dye 1 2 Shade observed Brown Dark brown

Example 4: Examples of Dyeing in Basic Medium

[0200] The following dye compositions were prepared:

TABLE-US-00004 Dye 1 or 2 10.sup.−3 mol pH 9.5 dye support .sup.(3) Demineralized water qs 100 g .sup.(3): pH 9.5 dye support 96° ethyl alcohol 20.8 g Pentasodium salt of diethylenetriaminepentaacetic 0.48 g AM* acid as an aqueous 40% solution C.sub.8-C.sub.10 alkyl polyglucoside as an aqueous solution 3.6 g AM* at 60% by weight Benzyl alcohol 2.0 g Polyethylene glycol containing 8 units of ethylene 3.0 g oxide NH.sub.4Cl 4.32 g Aqueous ammonia containing 20% NH.sub.3 2.94 g *AM: Active Material

[0201] Each mixture obtained was applied to locks of grey hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

[0202] The hair colouring is evaluated visually and/or measured.

[0203] The shades obtained are given in the table below:

TABLE-US-00005 Dye 1 2 Shade observed Dark brown Dark brown

[0204] For colourings in the presence of an oxidizing agent: at the time of use, each of the compositions described above was mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution. A final pH of 9.5 is obtained.

[0205] For colourings in oxidizing medium: at the time of use, each of the compositions described above was mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution. A final pH of 9.5 is obtained.

[0206] The shades obtained are given in the table below:

TABLE-US-00006 Dye 1 2 Shade observed Dark brown Dark brown

[0207] The colour of the locks was evaluated in the CIE L* a* b* system, using a Minolta Spectrophotometer CM2600D colorimeter (specular components included, illuminant D65, angle 10°).

[0208] In this L* a* b* system, the three parameters denote, respectively, L*: the colour intensity, a*: the green/red colour axis, and b*: the blue/yellow colour axis. For the intensity, the lower the value, the darker and more intense the colour.

[0209] The results are given in the table below:

TABLE-US-00007 Dye L* a* b* 1 26.57 3.53 7.72