CATIONIC BENZOXAZINE DERIVATIVES AND USE IN HAIR DYEING

Abstract

The invention relates to novel cationic benzoxazine-based compounds of formula (I) below, in which •R represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 hydroxyalkyl radical, •—R.sub.2, R.sub.3, R.sub.4 and R.sub.5 independently represent: —a hydrogen atom, —a linear C.sub.1-C.sub.4 or branched C.sub.3-C.sub.4 alkyl radical, optionally substituted with a hydroxyl radical, •L represents a linear or branched, saturated C.sub.1-C.sub.30 hydrocarbon-based chain, •CAT+ represents a cationic radical chosen from: —a cationic heterocyclic radical comprising 5 to 8 ring members containing at least one heteroatom chosen from O, N and S, —a tri(hydroxy)(C.sub.1-C.sub.4)alkylammonium radical, —a non-cationic heterocycle comprising 5 or 6 ring members containing at least one heteroatom chosen from O and N, such as pyrrolidine, substituted with a cationic radical, An− represents an anion or a mixture of anions which are organic or inorganic and are cosmetically acceptable.

##STR00001##

Claims

1. Compound of formula (I) below, addition salts thereof, optical isomers, geometrical isomers and tautomers thereof and/or solvates thereof: ##STR00030## in which R represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 hydroxyalkyl radical; preferably, R represents a hydrogen atom, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 independently represent: a hydrogen atom, a linear C.sub.1-C.sub.4 or branched C.sub.3-C.sub.4 alkyl radical, optionally substituted with a hydroxyl radical, L represents a linear or branched, saturated C.sub.1-C.sub.30 hydrocarbon-based chain, optionally substituted with one or more hydroxyl radicals, optionally interrupted with one or more non-adjacent oxygen atoms or with one or more non-adjacent radicals NR′, R′ denoting a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical, CAT+ represents a cationic radical chosen from: a cationic heterocyclic radical comprising 5 to 8 ring members containing at least one heteroatom chosen from O, N and S, optionally substituted with one or more radicals, which may be identical or different, chosen from linear or branched C.sub.1-C.sub.4 alkyl radicals or linear or branched C.sub.1-C.sub.4 hydroxyalkyl radicals, a tri(hydroxy)(C.sub.1-C.sub.4)alkylammonium radical, a non-cationic heterocycle comprising 5 or 6 ring members containing a heteroatom chosen from O and N, such as pyrrolidine, substituted with a cationic radical chosen from: imidazoliums, pyridiniums, piperaziniums, pyrrolidiniums, morpholiniums, pyrimidiniums, thiazoliums, benzimidazoliums, benzothiazoliums, oxazoliums, benzotriazoliums, pyrazoliums, triazoliums, benzoxazoliums and piperidiniums, which are optionally substituted with one or more identical or different radicals chosen from linear or branched C.sub.1-C.sub.4 alkyl radicals and linear or branched C.sub.1-C.sub.4 hydroxyalkyl radicals, or a tri(hydroxy)(C.sub.1-C.sub.4)alkylammonium radical, An− represents an anion or a mixture of anions which are organic or inorganic and are cosmetically acceptable.

2. Composition according to claim 1, characterized in that L represents a linear or branched, saturated C.sub.1-C.sub.20, preferably C.sub.1-C.sub.10, hydrocarbon-based chain, optionally substituted with one or more hydroxyl radicals, optionally interrupted with one or two non-adjacent oxygen atoms or non-adjacent radicals NR′, R′ denoting a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical.

3. Compound according to either of the preceding claims, characterized in that L represents a group: ##STR00031## in which: B represents an oxygen atom or a radical NR′ in which R′ represents a hydrogen atom or a C.sub.1-C.sub.4 alkyl radical, n represents an integer between 1 and 5, preferably n=1 or 2, AK represents a linear or branched, saturated C.sub.1-C.sub.10 hydrocarbon-based chain which is optionally substituted with one or more hydroxyl radicals, p=0, 1 or 2, when p is equal to 2, the radicals B respectively AK are identical or different, and the bond a links the group L to the cationic radical CAT+ and the bond b links the group L to the nitrogen atom of the oxazine ring.

4. Compound according to claim 3, characterized in that p=0 or 1.

5. Compound according to claim 3 or 4, characterized in that AK represents a linear or branched, saturated C.sub.1-C.sub.6 hydrocarbon-based chain, optionally substituted with one or more hydroxyl radicals, preferably a linear, saturated C.sub.1-C.sub.4 hydrocarbon-based chain.

6. Compound according to one of the preceding claims, characterized in that R′ represents H or CH.sub.3, preferably a hydrogen atom.

7. Compound according to one of the preceding claims, characterized in that L represents a linear, saturated C.sub.1-C.sub.6 hydrocarbon-based chain.

8. Compound according to one of claims 1 to 6, characterized in that L represents a linear C.sub.2-C.sub.10 alkyl radical, interrupted with an oxygen atom and/or with an —NH group.

9. Compound according to one of the preceding claims, characterized in that the cationic heterocyclic radical comprising 5 to 8 ring members containing at least one heteroatom chosen from O, N and S is chosen from imidazoliums, pyridiniums, piperaziniums, pyrrolidiniums, morpholiniums, pyrimidiniums, thiazoliums, benzimidazoliums, benzothiazoliums, oxazoliums, benzotriazoliums, pyrazoliums, triazoliums, benzoxazoliums and piperidiniums.

10. Compound according to one of the preceding claims, characterized in that the tri(hydroxy)(C.sub.1-C.sub.4)alkylammonium radical is chosen from trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, 2-hydroxyethyldiethylammonium, di-beta-hydroxyethylmethylammonium, tri-beta-hydroxyethylammonium, dimethylhydroxyethylammonium, 2-hydroxyethyldimethylammonium and 2-hydroxyethylmethylethylammonium.

11. Compound according to one of the preceding claims, characterized in that CAT+ represents a cationic radical chosen from: a cationic heterocyclic radical chosen from imidazoliums, piperaziniums, pyrrolidiniums, morpholiniums and piperidiniums which are optionally substituted with one or more identical or different radicals chosen from linear or branched C.sub.1-C.sub.4 alkyl radicals and linear or branched C.sub.1-C.sub.4 hydroxyalkyl radicals, a tri(hydroxy)(C.sub.1-C.sub.4)alkylammonium radical chosen from trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, 2-hydroxyethyldimethylammonium, diethylhydroxyethylammonium and 2-hydroxyethyldiethylammonium, a non-cationic heterocycle comprising 5 or 6 ring members containing a heteroatom chosen from O and N, such as pyrrolidine for example, substituted with a tri(hydroxy)(C.sub.1-C.sub.4)alkylammonium radical, for instance trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, 2-hydroxyethyldiethylammonium, 2-hydroxyethylmethylethylammonium, di-beta-hydroxyethylmethylammonium, tri-beta-hydroxyethylammonium, dimethylhydroxyethylammonium or 2-hydroxyethyldimethylammonium, in particular trimethylammonium or 2-hydroxyethylmethylethylammonium.

12. Compound according to one of the preceding claims, characterized in that CAT+ represents a cationic radical chosen from: a cationic heterocyclic radical chosen from imidazoliums, piperaziniums, pyrrolidiniums, morpholiniums and piperidiniums which are optionally substituted with one or more identical or different radicals chosen from linear or branched C.sub.1-C.sub.4 alkyl radicals and linear C.sub.1-C.sub.4 hydroxyalkyl radicals, a radical chosen from trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, 2-hydroxyethyldimethylammonium, 2-hydroxyethylmethylethylammonium, di-beta-hydroxyethylmethylammonium, tri-beta-hydroxyethylammonium, dimethylhydroxyethylammonium, and 2-hydroxyethyldimethylammonium, in particular trimethylammonium and 2-hydroxyethylmethylethylammonium, a pyrrolidine radical substituted with a trimethylammonium radical.

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

14. Compound according to one of the preceding claims, characterized in that R, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represent a hydrogen atom.

15. Compound of formula (I) according to one of the preceding claims, characterized in that it is chosen from the following compounds: ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## and also addition salts thereof, optical isomers, geometrical isomers and tautomers thereof and/or solvates thereof.

16. Use of a compound chosen from the compounds of formula (I) as defined in one of claims 1 to 15, for dyeing keratin fibres, in particular human keratin fibres such as the hair.

17. Process for dyeing keratin fibres, in particular the hair, which consists in applying to said fibres a composition comprising a compound of formula (I) according to one of claims 1 to 15.

18. Composition, in particular cosmetic composition, comprising at least one benzoxazine-based compound of formula (I) according to one of claims 1 to 15.

Description

EXAMPLES

Synthesis of the structural distributor A=2-(7-nitro-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl methanesulfonate

[0189] ##STR00026##

[0190] 100 ml of dichloromethane, 6.7 g (0.030 mol) of 2-(7-nitro-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethanol and 6.8 g (0.06 mol) of mesyl chloride are successively placed in a 100 ml three-necked flask equipped with a thermometer, a condenser, a bubbler and a dropping funnel, with magnetic stirring. 6 g (0.060 mol) of triethylamine are added dropwise to this solution. This clear solution is stirred at ambient temperature for 16 hours.

[0191] The organic phase is washed with water and dried over anhydrous magnesium sulfate, and the solvent is evaporated off to give a crude product, which, after purification by recrystallization from ethyl acetate, gives 6.8 g (72% yield) of expected compound A in the form of a yellow powder.

[0192] The NMR (.sup.1H 400 MHz and .sup.13C 100.61 MHz DMSO-d.sub.6) and mass spectrometry analyses are in accordance with the expected structure.

[0193] The mass spectrometry analysis confirms the expected compound C11H14N2O6. The quasi-molecular ions [M+H]+, [M+Na]+, [M−H]− of the expected molecule are mainly detected.

Example 1: Synthesis of 1-[2-(7-amino-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl]-3-methyl-1H-imidazol-3-ium methanesulfonate hydrochloride

[0194] ##STR00027##

Synthesis of 3-methyl-1-[2-(7-nitro-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl]-1H-imidazol-3-ium methanesulfonate

[0195] ##STR00028##

[0196] 300 ml of tetrahydrofuran, 2 g (0.066 mol) of structural distributor “A” 2-(7-nitro-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl methanesulfonate and then 1.58 ml (0.07 mol) of methylimidazole are successively added, dropwise, to a 50 ml three-necked flask equipped with a thermometer, a condenser, a bubbler and a dropping funnel, with magnetic stirring. The homogeneous medium is heated for 30 minutes. The precipitate formed is isolated by filtration after cooling to ambient temperature.

[0197] The solid formed is recovered and dried under vacuum at 30° C. in the presence of desiccant, and gives 2.15 g (84.6% yield) of expected compound in the form of a yellow powder.

[0198] The NMR analyses (1D 1H and 2D 1H/13C NMR spectra of HMBC type) are in accordance with the expected structure.

Synthesis of 1-[2-(7-amino-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl]-3-methyl-1H-imidazol-3-ium methanesulfonate hydrochloride

[0199] ##STR00029##

[0200] A solution resulting from 5 g (0.0165 mol) of 3-methyl-1-[2-(7-nitro-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl]-1H-imidazol-3-ium methanesulfonate in 1000 ml of absolute ethanol is introduced at a flow rate of 3 ml per minute onto a cartridge of palladium catalyst at 80° C. under a pressure of 50 bar in the H-Cube system in the presence of hydrogen.

[0201] At the machine outlet, the solution obtained is added to a solution of 75 ml of 6N hydrochloric isopropanol under argon.

[0202] The light-grey solid formed is recovered by filtration and is dried under vacuum at 30° C. in the presence of desiccant, to give 4.4 g (84.3% yield) of expected compound in the form of a light-grey powder.

[0203] The NMR analyses (1D 1H and 2D 1H/13C NMR spectra of HMBC type) are in accordance with the expected structure.

Example 2: Dye Compositions

[0204] The following dye compositions were prepared:

TABLE-US-00001 Example A B C D E 1-[2-(7-Amino-2,3- 10.sup.−3 mol 10.sup.−3 mol 10.sup.−3 mol 10.sup.−3 mol 10.sup.−3 mol dihydro-4H-1,4- benzoxazin-4-yl)ethyl]-3- methyl-1H-imidazol-3-ium methanesulfonate hydrochloride 2-(2,4- 10.sup.−3 mol diaminophenoxy)ethanol hydrochloride 5-Amino-2-methylphenol 10.sup.−3 mol 2-METHYL-5- 10.sup.−3 mol HYDROXYETHYLAMINO PHENOL 6- 10.sup.−3 mol HYDROXYBENZOMORPHOLINE 2-AMINO-3- 10.sup.−3 mol HYDROXYPYRIDINE Dye support (1) (*) (*) (*) (*) (*) Demineralized water qs 100 g 100 g 100 g 100 g 100 g Shade observed Blue Chestnut light dark dark green Brown brown brown purple ash brown (*): dye support (1) pH 9.5 96° ethyl alcohol 20.8 g 35% aqueous sodium metabisulfite solution 0.23 g AM Pentasodium salt of diethylenetriaminepentaacetic acid as an aqueous 0.48 g AM 40% solution C.sub.8-C.sub.10 alkyl polyglucoside as an aqueous 60% solution 3.6 g AM Benzyl alcohol 2.0 g Polyethylene glycol containing 8 units of ethylene oxide 3.0 g NH.sub.4Cl 4.32 g Aqueous ammonia containing 20% NH.sub.3 2.94 g

[0205] At the time of use, each composition is mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight). A final pH of 9.5 is obtained.

[0206] Each mixture obtained is applied to locks of grey hair containing 90% white hairs. After a leave-in time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried, to give the shades mentioned.