Use of substituted dihydroisoquinolinium salts for treating keratin materials, compositions and implementation processes

Abstract

The present invention relates to the use of one or more particular dihydroisoquinolinium salts of formula (I) for treating keratin materials, in particular keratin fibres, especially human keratin fibres such as the hair. The invention also relates to a process for treating keratin materials using said salts and optionally one or more chemical oxidizing agents. A subject of the invention is also a composition for lightening keratin materials, comprising one or more dihydroisoquinolinium salts and one or more chemical oxidizing agents. The present invention also relates to one or more particular dihydroisoquinolinium salts and also to compositions containing them, in particular compositions comprising a physiologically acceptable medium. ##STR00001##

Claims

1. A method for treating keratin materials comprising applying to said keratin materials, optionally in the presence of one or more chemical oxidizing agents, at least one compound chosen from: (a) compounds of formula (I), the addition salts thereof, or the solvates thereof: ##STR00022## wherein in formula (I): R is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, cyano, or amino —NR.sub.10R.sub.11 groups; R.sub.1 is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9, are chosen from, independently of each other, a radical chosen from: a hydrogen atom, a halogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups, a C.sub.1-C.sub.6 alkoxy radical, a hydroxyl radical, an amino radical —NR.sub.10R.sub.11, or an aminocarbonyl radical —CONH.sub.2; R.sub.10 and R.sub.11, which may be identical or different, are chosen from a hydrogen atom or a linear or branched C.sub.1-C.sub.6 alkyl radical; with the proviso that R, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 cannot all be identical; and An.sup.− represents an organic or mineral anion or mixture of anions which ensures the electrical neutrality of the compounds of formula (I); or (b) 2,3,3-trimethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (Compound 2): ##STR00023##

2. The method according to claim 1, wherein R.sub.4, R.sub.5, R.sub.6 and R.sub.9 are identical and represent a hydrogen atom.

3. The method according to claim 1, wherein R.sub.7 and R.sub.8 are identical and represent a hydrogen atom or a C.sub.1-C.sub.6 alkoxy radical.

4. The method according to claim 1, wherein the compound of formula (I) is chosen from the compounds of formula (II), the addition salts thereof, or the solvates thereof: ##STR00024## wherein in formula (II): R is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, cyano, or amino —NR.sub.10R.sub.11 groups; R.sub.1 is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are chosen from, independently of each other, a radical chosen from: a hydrogen atom, a halogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups, or an aminocarbonyl radical —CONH.sub.2; R.sub.10 and R.sub.11, which may be identical or different, are chosen from a hydrogen atom or a linear or branched C.sub.1-C.sub.6 alkyl radical; with the proviso that R, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 cannot all be identical; and An.sup.− represents an organic or mineral anion or mixture of anions which ensures the electrical neutrality of the compounds of formula (II).

5. The method according to claim 4, wherein R.sub.2 and R.sub.3 are identical and represent a hydrogen atom or a linear or branched C.sub.1-C.sub.6 alkyl radical, optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups.

6. The method according to claim 4, wherein R.sub.4 and R.sub.5 are identical and represent a hydrogen atom.

7. The method according to claim 4, wherein R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are identical and represent a hydrogen atom.

8. The method according to claim 1, wherein the compound of formula (I) is chosen from the following compounds: TABLE-US-00007 1,2,3,3-tetramethyl- 3,4-dihydroisoquinolinium toluenesulfonate (Compound 1) 6,7-dimethoxy- 1,2-dimethyl-,3,4- dihydroisoquinolinium toluene-4-sulfonate (Compound 3) 1-(cyanomethyl)-2- methyl-3,4- dihydroisoquinolinium tetrafluoroborate (Compound 4) or mixtures thereof.

9. A method for improving the oxidizing activity of at least one chemical oxidizing agent, the method comprising combining at least one chemical oxidizing agent with a compound chosen from: (a) compounds of formula (I), the addition salts thereof, or the solvates thereof: ##STR00028## wherein in formula (I): R is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, cyano, or amino —NR.sub.10R.sub.11 groups; R.sub.1 is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9, are chosen from, independently of each other, a radical chosen from: a hydrogen atom, a halogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups, a C.sub.1-C.sub.6 alkoxy radical, a hydroxyl radical, an amino radical —NR.sub.10R.sub.11, or an aminocarbonyl radical —CONH.sub.2; R.sub.10 and R.sub.11, which may be identical or different, are chosen from a hydrogen atom or a linear or branched C.sub.1-C.sub.6 alkyl radical; with the proviso that R, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 cannot all be identical; and An.sup.− represents an organic or mineral anion or mixture of anions which ensures the electrical neutrality of the compounds of formula (I); or (b) 2,3,3-trimethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (Compound 2): ##STR00029##

10. A composition comprising: at least one chemical oxidizing agent, and at least one compound; wherein the at least one compound is chosen from: (a) compounds of formula (I), the addition salts thereof, or the solvates thereof: ##STR00030## wherein in formula (I): R is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, cyano, or amino —NR.sub.10R.sub.11 groups; R.sub.1 is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9, are chosen from, independently of each other, a radical chosen from: a hydrogen atom, a halogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups, a C.sub.1-C.sub.6 alkoxy radical, a hydroxyl radical, an amino radical —NR.sub.10R.sub.11, or an aminocarbonyl radical —CONH.sub.2; R.sub.10 and R.sub.11, which may be identical or different, are chosen from a hydrogen atom or a linear or branched C.sub.1-C.sub.6 alkyl radical; with the proviso that R, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 cannot all be identical; and An.sup.− represents an organic or mineral anion or mixture of anions which ensures the electrical neutrality of the compounds of formula (I); or (b) 2,3,3-trimethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (Compound 2): ##STR00031##

11. The composition according to claim 10, wherein the at least one chemical oxidizing agent is hydrogen peroxide.

12. A compound chosen from: (a) compounds of formula (II), the addition salts thereof, or the solvates thereof: ##STR00032## wherein in formula (II): R is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, cyano, or amino —NR.sub.10R.sub.11 groups; R.sub.1 is chosen from: a linear or branched C.sub.1-C.sub.12 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, cyano, or amino —NR.sub.10R.sub.11 groups; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are chosen from, independently of each other, a radical chosen from: a hydrogen atom, a halogen atom, a linear or branched C.sub.1-C.sub.6 alkyl radical optionally substituted with at least one group, which may be identical or different, chosen from hydroxyl, C.sub.1-C.sub.6 alkoxy, or amino —NR.sub.10R.sub.11 groups, or an aminocarbonyl radical —CONH.sub.2; R.sub.10 and R.sub.11, which may be identical or different, are chosen from a hydrogen atom or a linear or branched C.sub.1-C.sub.6 alkyl radical; with the proviso that R, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 cannot all be identical; and An.sup.− represents an organic or mineral anion or mixture of anions which ensures the electrical neutrality of the compounds of formula (II); or (b) 2,3,3-trimethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (Compound 2): ##STR00033## wherein the compound is not chosen from the following compounds: ##STR00034## ##STR00035##

13. The compounds of formula (II) according to claim 12, chosen from 1,2,3,3-tetramethyl-3,4-dihydroisoquinolinium toluenesulfonate, 6,7-dimethoxy-1,2-dimethyl-,3,4-dihydroisoquinolinium toluene-4-sulfonate, or 1-(cyanomethyl)-2-methyl-3,4-dihydroisoquinolinium tetrafluoroborate.

14. A composition comprising at least one compound according to claim 12, the addition salts thereof, or the solvates thereof.

Description

EXAMPLES

Example 1

Synthesis of 1,2,3,3-tetramethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (Compound 1)

(1) ##STR00011##

Step 1: Synthesis of 1,3,3-trimethyl-3,4-dihydroisoquinoline (a)

(2) ##STR00012##

(3) 100.6 ml of concentrated sulfuric acid (9.4 eq.) are placed in a 500 ml three-necked flask equipped with a condenser and a thermometer, followed by cooling to a temperature in the region of 5-10° C. A mixture containing 30 g of methyl-1-phenyl-2-propanol (1 eq.) and 9.83 g of acetonitrile (1 eq.) is added dropwise. The mixture is stirred for 5 minutes at a temperature in the region of 5-10° C. and then for 5 hours at room temperature (monitoring by TLC, 95/5 CH.sub.2Cl.sub.2/MeOH).

(4) The mixture is then poured into 1 litre of water and extracted with 100 ml of toluene. The aqueous phase is basified to pH 8.5 with ammonium carbonate and then extracted twice with 500 ml of MTBE (methyl tert-butyl ether). The organic phase is dried over Na.sub.2SO.sub.4, filtered, evaporated to dryness and then dried under vacuum over P.sub.2O.sub.5.

(5) 27 g (78% yield) of compound (a) are obtained in the form of a yellow liquid.

(6) The NMR and mass analyses are in accordance with the expected structure.

Step 2: Synthesis of 1,2,3,3-tetramethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (1)

(7) ##STR00013##

(8) 13 g of 1,3,3-trimethyl-3,4-dihydroisoquinoline (a) (1 eq.) and 14.25 g (1.02 eq.) of para-toluenesulfonyl methyl ester are placed in a 100 ml three-necked flask. The mixture is heated under argon at a temperature of 110° C. for 24 hours.

(9) The resulting crude product is then purified on a column of silica, and 17.5 g of 1,2,3,3-tetramethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (1) are obtained (yield=65%).

(10) The NMR and mass analyses are in accordance with the expected structure.

Example 2

Synthesis of 2,3,3-trimethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (Compound 2)

(11) ##STR00014##

(12) ##STR00015##

(13) 26.98 g of 2,3,3-trimethyl-3,4-dihydroisoquinolinium iodide (1 eq.) are placed in 250 ml of demineralized water in a 500 ml three-necked flask equipped with a condenser and a thermometer.

(14) 25 g of silver tosylate (1 eq.) are then added, protected from light. The mixture is left overnight at room temperature (monitoring by TLC, 95/5 CH.sub.2Cl.sub.2/MeOH).

(15) A yellow precipitate is filtered off. The filtrate is evaporated to dryness and the oil crystallizes once dried under vacuum over P.sub.2O.sub.5. 6.2 g (100% yield) of compound 2 are obtained in the form of a hardening yellow oil.

(16) The NMR and mass analyses are in accordance with the expected structure.

Example 3

Synthesis of 6,7-dimethoxy-1,2-dimethyl-3,4-dihydroisoquinolinium toluene-4-sulfonate (Compound 3)

(17) ##STR00016##

(18) ##STR00017##

(19) 20 g of 1-methyl-6,7-dimethoxy-3,4-dihydroisoquinoline (1 eq.) and 18.5 g (1.02 eq.) of para-toluenesulfonyl methyl ester are placed in 70 ml of toluene in a 100 ml three-necked flask. The mixture is heated under argon at a temperature of 60° C. for 4 hours. A brown precipitate is filtered off and washed with acetone. 3.4 g (98% yield) of compound (3) are obtained in the form of a yellow powder.

(20) The NMR and mass analyses are in accordance with the expected structure.

Example 4

Synthesis of 1-(cyanomethyl)-2-methyl-3,4-dihydroisoquinolinium tetrafluoroborate (Compound 4)

(21) ##STR00018##

(22) ##STR00019##

(23) 4.78 g (1.1 eq.) of trimethyloxonium tetrafluoroborate (Meerwein's salt) are placed in 80 ml of dichloromethane in a 100 ml three-necked flask. The mixture is cooled to a temperature of 0° C. A solution containing 5 g of 1-(cyanomethyl)-2-methyl-3,4-dihydroisoquinoline (1 eq.) in 50 ml of dichloromethane is then added dropwise. The reaction medium is then left at room temperature for 2 days. A yellow precipitate is filtered off and washed with diisopropyl ether. 5.05 g (63% yield) of compound (4) are obtained in the form of a yellow powder.

(24) The NMR and mass analyses are in accordance with the expected structure.

(25) Examples of Compositions and Evaluation

Example 5

(26) In this example, the effect of improving the oxidizing power afforded by the dihydroisoquinolinium salts according to the invention is studied.

(27) I. Preparation of Synthetic Melanin

(28) The synthetic melanin used for the evaluation is obtained by polymerizing 5,6-dihydroxyindole with hydrogen peroxide according to the following procedure:

(29) 100 g of 5,6-dihydroxyindole are placed in 456 g of water heated to a temperature of 80° C. After stirring for 10 minutes, 1 ml of 20% aqueous ammonia solution is added and the medium is then maintained for 30 minutes at a temperature of 80° C. 152 g of 30% hydrogen peroxide are then added dropwise and stirring is continued for 2.5 hours at 80° C. After cooling, the suspension formed is filtered and washed with water.

(30) 86 g of synthetic melanin are thus obtained.

(31) II. Compositions Tested

(32) The compositions used in this example were obtained from the following ingredients (the percentages indicated are weight percentages relative to the total weight of the composition).

(33) Compositions B and C are compositions according to the invention.

(34) TABLE-US-00001 Composition A Composition B Composition C H.sub.2O.sub.2 1 ml  1 ml  1 ml 1,2,3,3-Tetramethyl- — 60 mg — 3,4- dihydroisoquinolinium toluene-4-sulfonate (compound 1) 2,3,3-Trimethyl-3,4- — — 40.5 mg dihydroisoquinolinium toluene-4-sulfonate (compound 2) Water qs 100 qs 100 qs 100

(35) III. Procedure

(36) The following procedure is applied for each composition described in the table in section II.

(37) 1 ml of water, 1 ml of buffer of aqueous ammonia and ammonium chloride at pH 9.5 and 1 ml of the studied composition (compositions A, B and C) are applied to 1 mg of synthetic melanin obtained in accordance with section I.

(38) The lightening (L*) obtained after 20 minutes of incubation at a temperature of 22° C. followed by 30 minutes at a temperature of 30° C. is measured using a Biotec Power Wave 200 spectrocolorimeter.

(39) IV. Results

(40) TABLE-US-00002 Composition A Composition B Composition C Lightening 56 79 80 (L*)

(41) It is noted that greater lightening is obtained with compositions B and C according to the invention than with composition A.

(42) In particular, it is noted that the presence of the dihydroisoquinolinium salts makes it possible to improve the oxidizing power of hydrogen peroxide and thus to boost its activity (comparison between composition A and compositions B-C according to the invention).

Example 6

(43) I. Compositions Tested

(44) Composition (A) and oxidizing composition (B) have been prepared from the following ingredients (the percentages indicated are percentages by weight relative to the total weight of the composition).

(45) Composition (A):

(46) TABLE-US-00003 2-Octyldodecanol 11.5 Laureth-2 3 Polysorbate 21 11 Mineral oil/Paraffinum liquidum 74.5

(47) Oxidizing Composition (B):

(48) TABLE-US-00004 GLYCERIN 0.5 TRIDECETH-2 CARBOXAMIDE MEA 0.85 TETRASODIUM PYROPHOSPHATE 0.02 HYDROGEN PEROXIDE (50%) 12 SODIUM STANNATE 0.04 PENTASODIUM PENTETATE (40% in 0.15 water) CETEARYL ALCOHOL/CETEARETH-25 2.85 (80/20) WATER Qsp 100

(49) Compositions 1 (comparative) and 2 (invention) below were prepared by mixing 1 g of composition A, 1.5 g of the oxidizing composition B and by adding dihydroisoquinolinium dyes to be compared.

(50) TABLE-US-00005 Composition 1 Composition (comparative) 2 (invention) 0  30 mg — 2-methyl-3,4-dihydroisoquinolinium 4-methylbenzenesulfonate —  30 mg 1,2-dimethyl-3,4-dihydroisoquinolinium 4-methylbenzenesulfonate Composition (A)   1 g   1 g Oxidizing composition (B) 1.5 g 1.5 g Aqueous ammonia 20% NH.sub.4OH Qs pH = 9.5 Qs pH = 9.5

(51) II. Procedure

(52) After their preparation, compositions 1 and 2 are applied to natural 250 mg locks with a tone depth of 4. After a leave-on time of 30 minutes at a temperature of 27° C., the locks are washed, shampooed and dried.

(53) The lightening is measured using the CIE L*a*b* system with a Minolta CM-3610d Spectrophotometer (illuminant D65, angle 10°, specular component included). According to this system, L* indicates the lightness of the hair.

(54) The lightening is represented by the L*value: the higher the L* is, the better the lightening is.

(55) III. Results

(56) The results are summarized below:

(57) TABLE-US-00006 Composition 1 Composition 2 comparative invention Lightness 24.7 27.3 (L*)

(58) The results show that composition 2 according to the invention exhibits a better lightening than composition 1 (comparative).