PARA-PHENYLENEDIAMINE BASES WITH CATIONIC HETEROCYCLES, AND THE USE OF SAME FOR OXIDATION DYEING KERATIN FIBRES
20230144384 · 2023-05-11
Inventors
Cpc classification
C07D295/135
CHEMISTRY; METALLURGY
C07D233/64
CHEMISTRY; METALLURGY
C07D231/12
CHEMISTRY; METALLURGY
C07D233/61
CHEMISTRY; METALLURGY
A61K8/411
HUMAN NECESSITIES
A61K8/4946
HUMAN NECESSITIES
C07D207/325
CHEMISTRY; METALLURGY
C07D207/14
CHEMISTRY; METALLURGY
C07D207/20
CHEMISTRY; METALLURGY
International classification
C07D233/64
CHEMISTRY; METALLURGY
Abstract
The invention relates to primary para-phenylenediamine compounds substituted with an aliphatic chain comprising a cationic heterocyclic group according to formula (I), as well as the organic or mineral acid or base addition salts thereof, optical isomers, geometric isomers, tautomers, mesomers and/or solvates thereof, such as hydrates. Formula (I), wherein: ALK is a linear or branched, optionally substituted, alkylene chain comprising 3 to 8 carbon atoms; HET.sup.+ is a saturated or unsaturated, aromatic or non-aromatic cationic heterocyclic group, optionally substituted, comprising 5 to 0 links, optionally substituted, and comprising one or more ammonium groups; and An.sup.−, present or absent, is a mineral or organic anionic counterion ensuring the electroneutrality of the molecule. The present invention also relates to a composition comprising one or more of these previously defined compounds, in a medium suitable for dyeing. The present invention lastly relates to a dyeing device consisting of a first compartment which contains said composition, and a second compartment containing one or more oxidising agents.
##STR00001##
Claims
1. -20. (canceled)
21. A compound chosen from compounds of formula (I) below: ##STR00045## addition salts thereof with organic or inorganic acids or bases, optical isomers thereof, geometric isomers thereof, tautomers thereof, mesomers thereof, or solvates thereof: wherein: ALK represents a linear or branched alkylene chain comprising from 3 to 8 carbon atoms which is optionally substituted; HET.sup.+ represents a saturated or unsaturated, aromatic or non-aromatic cationic heterocyclic group, which is optionally substituted, comprising from 5 to 10 ring members, and comprising one or more ammonium groups; and An.sup.−, which is present or absent, represents an inorganic or organic anionic counterion, ensuring the electrical neutrality of the molecule.
22. The compound of claim 21, wherein ALK represents a linear unsubstituted C.sub.3-C.sub.6 alkylene chain.
23. The compound of claim 21, wherein HET.sup.+ is an aromatic or non-aromatic, monocyclic or bicyclic, fused or non-fused heterocyclic group which contains one or more unsaturations, comprising from 5 to 10 ring members, and from 1 to 4 heteroatoms chosen from a nitrogen, oxygen, or sulfur atom; and further comprising one or more =N.sup.+(R.sub.e)—; —N.sup.+(R.sub.e)(R.sub.f)—; and/or —N.sup.+(R.sub.e)(R.sub.f)(R.sub.g) ammonium groups being borne by one or more substituents of the heterocycle or else said —N.sup.+(R.sub.e)(R.sub.f)(R.sub.g) ammonium group(s) being one or more substituents of the heterocycle, with R.sub.e, R.sub.f, R.sub.g independently denoting a (C.sub.1-C.sub.6)alkyl radical or a hydroxy(C.sub.1-C.sub.6)alkyl radical; said cationic heterocyclic radical being chosen from: i) cationic heterocycles, at least one of the ring members of which is an =N.sup.+(R.sub.e)—, or —N.sup.+(R.sub.e)(R.sub.f)— ammonium radical; ii) heterocycles substituted by a radical bearing an —N.sup.+(R.sub.e)(R.sub.f)(R.sub.g) cationic group; and ii) heterocycles substituted by an —N.sup.+(R.sub.e)(R.sub.f)(R.sub.g) cationic radical I.
24. The compound of claim 21, wherein HET.sup.+ is chosen from the formulae (A) to (P) below: ##STR00046## ##STR00047## wherein n being equal to 1, 2 or 3; m and t, which are identical or different, being equal to 1, 2, or 3; R.sup.1, R.sup.1′ and R.sup.2, which are identical or different, represent a (C.sub.1-C.sub.6)alkyl group, or a hydroxy(C.sub.1-C.sub.6)alkyl group; R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, which are identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio, (di)(C.sub.1-C.sub.6)(alkyl)amino, nitro(so), R.sup.8—(Z′).sub.p—C(Z″)—(Z″′).sub.q— with p and q, which are identical or different, being equal to 0 or 1, Z′, Z″ and Z″′, which are identical or different, representing an oxygen atom, a sulfur atom or an N(R.sup.9) group with R.sup.8 and R.sup.9, which are identical or different, representing a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group or a hydroxy(C.sub.1-C.sub.4)alkyl group; or two contiguous chosen from R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.8 and R.sup.9, form, together with the carbon atoms which bear them, a benzo group; X and Y, which are identical or different, represent a nitrogen atom, or a group chosen from C(R.sup.8) with R.sup.8 or R.sup.8 represents an (C.sub.1-C.sub.4)alkylcarbonyl group; Z representing an oxygen atom, a sulfur atom, a C(R.sup.8)(R.sup.9) group, or N(R.sup.9) group with R.sup.8 and R.sup.9; ALK' represents a linear or branched (C.sub.1-C.sub.4)alkylene group, which is optionally substituted; ##STR00048## represents the part of the group linked to the rest of the molecule; and - - - - - representing a single bond or double bond; wherein for (O) and (P) the (R.sup.1)(R′.sub.1)(R.sup.2)N.sup.+— and (R.sup.1)(R′.sub.1)(R.sup.2)N.sup.+-ALK′-ammonium groups respectively are optionally borne by Z when Z represents a C(R.sup.8)(R.sup.9) group, in which case one of the two R.sup.8 or R.sup.9 groups is absent.
25. The compound of claim 21, wherein HET.sup.+ is chosen from (A) and (B) with n being equal to 1 or 2.
26. The compound of claim 23, wherein HET.sup.+ represents the (A.sub.1) group: ##STR00049## wherein R.sup.1 and R.sup.2, which are identical or different, representing a (C.sub.1-C.sub.4)alkyl group.
27. The compound of claim 24, wherein HET.sup.+ represents the group chosen from (B.sub.1), (B.sub.2), (B.sub.3), (B.sub.4), or (B.sub.5) below: ##STR00050## with R.sup.1 and R.sup.9, which are identical or different, representing a (C.sub.1-C.sub.4)alkyl group; ##STR00051## with R.sup.1 representing a (C.sub.1-C.sub.4)alkyl group; ##STR00052## with R.sup.1 representing a (C.sub.1-C.sub.4)alkyl group; ##STR00053## with R.sup.1 representing a (C.sub.1-C.sub.4)alkyl group; ##STR00054## with R.sup.1 representing a (C.sub.1-C.sub.4)alkyl group.
28. The compound of claim 24, wherein HET.sup.+ represents the (C.sub.1) group below: ##STR00055##
29. The compound of claim 24, wherein HET.sup.+ represents the imidazolium group (D.sub.1) or the mesomeric form thereof (D′1): ##STR00056## wherein R.sup.3 and R.sup.4 represent a hydrogen atom and R.sup.1 represents a (C.sub.1-C.sub.4)alkyl group. ##STR00057##
30. The compound of claim 24, wherein HET.sup.+ represents the pyrazolium group (E.sub.1): ##STR00058## wherein R.sup.3, R.sup.4 and R.sup.8 represent a hydrogen atom and R.sup.1 represents a (C.sub.1-C.sub.4)alkyl group.
31. The compound of claim 24, wherein HET.sup.+ represents the pyrrolium group (F.sub.1): ##STR00059## wherein R.sup.3, R.sup.4 and R.sup.8 represent a hydrogen atom and R.sup.1 represents a (C.sub.1-C.sub.4)alkyl group.
32. The compound of claim 24, wherein HET.sup.+ represents the pyrrolinium group (O.sub.1): ##STR00060## wherein R.sup.1, R′.sup.1, and R.sup.2, represent a (C.sub.1-C.sub.4)alkyl group, n is equal to 1 or 2, wherein the (R.sup.1)(R′.sub.1)(R.sup.2)N.sup.+-ammonium group is in position 2, 3, or 4.
33. The compound of claim 24, wherein HET.sup.+ represents the pyrrolidinyl group (Pi): ##STR00061## wherein R.sup.1, R′.sup.1, and R.sup.2, represent a (C.sub.1-C.sub.4) group, n is equal to 1 or 2, ALK′ represents a linear (C.sub.1-C.sub.4)alkylene group, wherein the (R.sup.1)(R′.sub.1)(R.sup.2)N.sup.+-ALK-group is in position 2, 3, or 4.
34. The compound of claim 21, wherein the compound is chosen from compounds 1 to 13, inorganic or organic acid salts thereof, mesomers thereof, tautomers thereof, or solvates thereof: TABLE-US-00016 Compound 1
35. A method of oxidation dyeing of keratin fibers comprising applying to the keratin fibers a compound chosen from compounds of formula (I) below: ##STR00075## addition salts thereof with organic or inorganic acids or bases, optical isomers thereof, geometric isomers thereof, tautomers thereof, mesomers thereof, or solvates thereof: wherein: ALK represents a linear or branched alkylene chain comprising from 3 to 8 carbon atoms which is optionally substituted; HET.sup.+ represents a saturated or unsaturated, aromatic or non-aromatic cationic heterocyclic group, which is optionally substituted, comprising from 5 to 10 ring members, and comprising one or more ammonium groups; and An.sup.−, which is present or absent, represents an inorganic or organic anionic counterion, ensuring the electrical neutrality of the molecule.
36. A composition for dyeing keratin fibers, comprising, in a medium appropriate for dyeing, at least one compound of claim 21.
37. The composition of claim 36, wherein the composition further comprises one or more couplers chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers, heterocyclic couplers, addition salts thereof, or mixtures thereof.
38. The composition of claim 37, wherein the composition further comprises at least one oxidizing agent chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids, or oxidase enzymes.
39. A method of dyeing keratin fibers, comprising applying to the keratin fibers the composition of claim 36.
40. A process for the preparation of a compound of formula (I) below: ##STR00076## wherein: ALK represents a linear or branched alkylene chain comprising from 3 to 8 carbon atoms which is optionally substituted; HET.sup.+ represents a saturated or unsaturated, aromatic or non-aromatic cationic heterocyclic group, which is optionally substituted, comprising from 5 to 10 ring members, and comprising one or more ammonium groups; and An.sup.−, which is present or absent, represents an inorganic or organic anionic counterion, ensuring the electrical neutrality of the molecule; comprising: ##STR00077## wherein Nu represents a Nucleophilic group comprising the cationic group HET.sup.+ , ALK.sub.−1 represents a linear or branched alkylene chain comprising from 2 to 7 carbon atoms which is optionally substituted, LG represents a leaving group, and PG represents a protecting group resistant to the reaction conditions throughout the synthesis up to the deprotection step; which process consists: either, in a first step i), in reducing the bicyclic amido derivative (a) in order to result in the 4-nitroaniline compound substituted in the a position with respect to the amino by a hydroxypropyl group (b); then, in a second step ii), in transforming the hydroxyl group of the compound (b) into a leaving group LG such as halogen, triflate, tosylate, mesylate, via a (C.sub.1-C.sub.6)alkylsulfonyl halide, step ii) performed in a polar or non-polar protic solvent; then, in a third step iii), in substituting the leaving group LG with a cationic group HET.sup.+ ; then, in a fourth step iv), in reducing the nitro compound (d) by catalytic hydrogenation, in order to result in the compound of formula (I); or, in a second step v), in reducing the 4-nitroaniline derivative substituted in the a position with respect to the amino by a hydroxypropyl group (b), by catalytic hydrogenation, in order to result in the 1,4-phenylenediamine compound substituted in the a position with respect to the amino by a hydroxypropyl group (e), then, in a third step vi), in protecting the amino groups with a protecting group, via a reagent such as R—C(Y.sub.a)—Y.sub.a—C(Y.sub.a)—R′, with R and R′, which are identical or different, representing a (C.sub.1-C.sub.6)alkyl group and Ya, which is identical or different, representing an oxygen or sulfur atom; followed by steps vii) and viii) of substitutions 1 and 2 under the same conditions as during steps ii) and iii), in order to result in the compounds (c) and (d) respectively, and then the compound (h) is deprotected, in an organic solvent.
Description
EXAMPLES
Examples of Syntheses
Example 1
synthesis of 1-[3-(2,5-diaminophenyl)propyl]-3-methyl-1H-imidazol-3-ium chloride dihydrochloride
[0120] ##STR00038##
Example 2
synthesis of 4-[3-(2,5-diaminophenyl)propyl]-1,1-dimethylpiperazin-1-ium chloride dihydrochloride
[0121] ##STR00039##
##STR00040##
[0122] Preparation of the intermediate: synthesis of N,N′-[2-(3-chloropropyl)benzene-1,4-diyl]diacetamide
##STR00041##
[0123] The synthesis of N,N′-[2-(3-hydroxypropyl)benzene-1,4-diyl]diacetamide may be carried out according to two processes starting from 3-(2,5-diaminophenyl)propan-1-ol dihydrochloride.
[0124] 1.sup.st process: 7.45 g of 3-(2,5-diaminophenyl)propan-1-ol dihydrochloride in 45 ml of water are introduced into a 250 ml three-necked flask equipped with a thermometer and a magnetic stirring bar, and then a solution of 6.22 g of sodium sulfite in 20 ml of water is added with stirring. 10 ml of acetic anhydride are then added dropwise to the reaction medium while cooling and then the mixture is left stirring at ambient temperature for 3 h. TLC (AcOEt/MeOH: 90/10) monitoring shows that the reaction is complete. The reaction medium is transferred into a flask containing 50 ml of n-BuOH. After stirring and separation of the two phases, the aqueous phase is extracted twice with n-BuOH. The combined organic phases are washed once with water and then once with saturated sodium chloride solution. After having been dried over anhydrous magnesium sulfate, the organic phase is concentrated under reduced pressure and a white powder is obtained which is then washed with hot ethyl acetate in order to result in the expected product N,N′-[2-(3-hydroxypropyl)benzene-1,4-diyl]diacetamide in the form of a white powder.
[0125] 2.sup.nd process: 100.62 g of 3-(2,5-diaminophenyl)propan-1-ol dihydrochloride in 500 ml of water are introduced into a 1 liter round-bottomed flask equipped with a dropping
[0126] funnel and a magnetic stirring bar, and then 58.0 g of sodium sulfite in 30 ml of water are added with stirring. 84 ml of acetic anhydride are added dropwise over 30 min while cooling and then the mixture is left stirring at ambient temperature for 3 h. TLC (AcOEt/MeOH: 90/10) monitoring shows that the reaction is not complete. A further 57 ml of acetic anhydride are added in three fractions and the mixture is left stirring at ambient temperature for 3 h after each addition. It is checked by TLC monitoring that the reaction is complete. The reaction medium (suspension) is filtered then the filtrate is transferred to a separating funnel and is extracted several times with AcOEt. The combined organic phases are concentrated under reduced pressure and the expected product is obtained in the form of a white powder after having been washed and dried.
##STR00042##
[0127] The synthesis of the intermediate N,N′-[2-(3-chloropropyl)benzene-1,4-diyl]diacetamide is carried out starting from N,N′-[2-(3-hydroxypropyl)benzene-1,4-diyl]diacetamide.
[0128] 60 g of N,N′-[2-(3-hydroxypropyl)benzene-1,4-diyl]diacetamide in 1150 ml of anhydrous THF are introduced into a 2 liter three-necked flask equipped with a thermometer, a dropping funnel and a magnetic stirring bar and a milky suspension is obtained. 50 ml of N,N-diisopropylethylamine in 30 ml of anhydrous THF are then added with stirring. 23 ml of methanesulfonyl chloride are added dropwise over 1 hour while cooling, and then the mixture is left stirring at ambient temperature before being refluxed until TLC (AcOEt/MeOH: 80/20) monitoring shows that the reaction is complete. The reaction medium is transferred into a mixture of water and AcOEt. The insoluble matter is filtered and, after washing and drying, a portion of the product is thus isolated in the form of a white powder. The filtrate is evaporated under reduced pressure and the residue is purified by flash chromatography on silica gel (eluent: 5/95˜10/90 MeOH/AcOEt). After removing the solvent, the expected product is also obtained in the form of a white powder.
Example 1
Synthesis of 1-[3-(2,5-diaminophenyl)propyl]-3-methyl-1H-imidazol-3-ium chloride dihydrochloride
[0129] ##STR00043##
[0130] 25 g of N,N′-[2-(3-chloropropyl)benzene-1,4-diyl]diacetamide in 450 ml of acetonitrile are introduced into a 1 liter three-necked flask equipped with a thermometer and a magnetic stirring bar and then 31 ml of methylimidazole are added with stirring to the suspension and the mixture is refluxed for 30 h. Since the reaction is incomplete (TLC monitoring), 10 ml of methylimidazole are added to the reaction medium and then the mixture is left stirring for an additional 10 h. The reaction medium is cooled to room temperature. The precipitate formed is filtered and washed with AcOEt, then dried in a desiccator. 1-{3-[2,5-Bis(acetylamino)phenyl]propyl}-3-methyl-1 H-imidazol-3-ium chloride is obtained in the form of a white powder.
[0131] 27.0 g of 1-{3-[2,5-bis(acetylamino)phenyl]propyl}-3-methyl-1 H-imidazol-3-ium chloride obtained previously in 250 ml of ethanol are introduced into a 1 liter three-necked flask equipped with a thermometer and a magnetic stirring bar, and 150 ml of 37% hydrochloric acid are carefully added. After refluxing for 4 h, the reaction is medium is evaporated under reduced pressure (rotary evaporator). The residue is taken up in isopropanol and again evaporated to dryness with a rotary evaporator. The residue is dissolved in a minimum of methanol and then this solution is poured dropwise into isopropanol. The precipitate obtained is filtered off and then washed with ethanol before being dried in a desiccator. 1-[3-(2,5-Diaminophenyl)propyl]-3-methyl-1H-imidazol-3-ium chloride dihydrochloride is obtained in the form of a beige powder.
Example 2
Synthesis of 4-[3-(2,5-diaminophenyl)propyl]-1,1-dimethylpiperazin-1-ium chloride dihydrochloride
[0132] ##STR00044##
[0133] 2.5 g of N,N′-[2-(3-chloropropyl)benzene-1,4-diyl]diacetamide in 30 ml of acetonitrile are introduced into a 100 ml three-necked flask equipped with a thermometer and a magnetic stirring bar and then 1.92 ml of 1,1-dimethylpiperazin-1-ium and 3.6 ml of N,N-diisopropylethylamine are added. After refluxing for 40 h, the reaction medium is filtered and the precipitate is washed with acetonitrile. The precipitate is taken up in acetonitrile and the mixture is stirred at 50° C. for 1 h, and then a hot filtration is carried out, before drying the precipitate in a desiccator. 4-{3-[2,5-Bis(acetylamino)phenyl]propyl}-1,1-dimethylpiperazin-1-ium chloride is obtained in the form of a beige powder. 2.5 g of the product obtained previously in 15 ml of ethanol and, carefully, 15 ml of 37% hydrochloric acid are introduced into a 100 ml three-necked flask equipped with a thermometer and a magnetic stirring bar. After refluxing for 5 h, the reaction medium is evaporated with a rotary evaporator. The residue is taken up in isopropanol and evaporated to dryness with a rotary evaporator. The residue is taken up in ethanol and after 30 min of stirring at 50° C., it is filtered then placed in a desiccator. 4-[3-(2,5-diaminophenyl)propyl]-1,1-dimethylpiperazin-1-ium chloride dihydrochloride is obtained in the form of a beige powder.
DYEING EXAMPLE
Example 1
Dye evaluation
[0134] Dyeing vehicle:
TABLE-US-00002 Compositions Amount Compound of formula (I) 0.05 mmol Oxidation coupler 0.05 mmol Water 7.0 ml Ethanol 2.0 ml 20% aqueous ammonia solution 1.0 ml 6-Volume aqueous hydrogen peroxide solution 1.0 ml
[0135] The following oxidation couplers were used:
TABLE-US-00003 Oxidation coupler Composition 3,4-dihydro-2H-1,4-benzoxazin-6-ol A1 5-[(2-hydroxyethyl)amino]-2-methylphenol A2 2-aminopyridin-3-ol A3 3-amino-2-chloro-6-methylphenol A4
[0136] Two series (S1) and (S2) of compositions (A1) to (A4) were therefore prepared. [0137] Each of the compositions (A1) to (A4) of the series (S1) comprises 1-[3-*(2,5-diaminophenyl)propyl]-3-methyl-1H-imidazol-3-ium chloride dihydrochloride (example 1). [0138] Each of the compositions (A1) to (A4) of the series (S2) comprises 4-[3-(2,5-diaminophenyl)propyl]-1,1-dimethylpiperazin-1-ium chloride dihydrochloride (example 2).
[0139] a) Procedure
[0140] Each composition (A1) to (A4) of each series (S1) and (S2) is applied to 1 g locks of natural Caucasian hair comprising 90% white hairs. After a leave-on time of 30 minutes at 27° C., the locks are rinsed, washed with a standard shampoo, rinsed again and then dried. The colorimetric data for each of the locks are then measured with a Minolta CM-3610d spectrophotometer.
[0141] b) Results
[0142] The following colorings were obtained:
[0143] Assessment of the dye evaluations of (S1) to (S2)
TABLE-US-00004 Composition S1 S2 A1 ash yellow light ash yellow A2 burgundy mauve A3 brown light brown A4 violet violet
Example 2
Evaluation of the Intensity and the Buildup: Invention vs. Comparative Composition
[0144] The comparative evaluation was carried out with the same dyeing vehicle as before, and according to the same operating conditions.
[0145] The oxidation bases are numbered as follows: [0146] B1 is 4-[3-(2,5-diaminophenyl)propyl]-1,1-dimethylpiperazin-1-ium chloride dihydrochloride (Invention) [0147] D is 2-[3-(4-methylpiperazin-1-yl)propyl]benzene-1,4-diamine tetrahydrochloride (Comparative composition)
[0148] The oxidation couplers are numbered as follows: [0149] C1 is 3,4-dihydro-2H-1,4-benzoxazin-6-ol [0150] C2 is 5-[(2-hydroxyethyl)amino]-2-methylphenol [0151] C3 is 2-aminopyridin-3-ol [0152] C4 is 3-amino-2-chloro-6-methylphenol
[0153] The colorimetric data for each of the locks are measured with a Minolta CM-3610d spectrophotometer. In this L*a*b* system, L* represents the lightness, a* indicates the green/red color axis and b* indicates the blue/yellow color axis.
[0154] The higher the value of L*, the lighter or less intense the color. Conversely, the lower the value of L*, the darker or more intense the color. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.
[0155] Evaluation of the Intensity L* of the Dyes
TABLE-US-00005 Bases D (comparative Couplers B1 (invention) composition) C1 49.94 56.11 C2 45.48 53.99 C3 46.86 57.99 C4 35.80 44.62
[0156] The color buildup on hair corresponds to the variation in coloring between the locks of dyed NG hair (natural gray hair containing 90% white hairs) and the non-dyed (i.e. untreated) NG hair, which is measured by (AE) according to the following equation:
ΔE=√{square root over ((L*−L.sub.o*).sup.2+(a*−a.sub.o*).sup.2+(b*−b.sub.o*).sup.2)}
[0157] In this equation, L*, a* and b* represent the values measured after dyeing of the NG hair, and L*, a.sub.o* and b.sub.o* represent the values measured before dyeing of the NG hair. The higher the ΔE value, the better the buildup of the coloring.
[0158] Evaluation of the Buildup ΔE of the Dyes
TABLE-US-00006 Bases D (comparative Couplers B1 (invention) composition) C1 10.36 4.95 C2 20.72 10.41 C3 15.75 3.84 C4 34.20 22.81
[0159] It is apparent from the above results that the colorings obtained with the method of is the invention are significantly more intense and more colorfast than those obtained with the comparative composition.
Example 3
Evaluation of the Intensity and the Buildup: Invention vs. Another Comparative Composition
[0160] Dyeing vehicle:
TABLE-US-00007 Ingredients Amount 2-Octyldodecanol 7.7 g Liquid petroleum jelly 50 g Oxyethylenated (2 OE) lauryl alcohol 2.0 g Oxyethylenated (4 OE) sorbitan monolaurate 7.3 g Water 33 g
[0161] Compositions:
TABLE-US-00008 Compositions Amount Oxidation base: para-phenylenediamine of 0.05 mmol formula (I) (invention) or comparative composition Oxidation coupler 0.05 mmol Oleogel vehicle 1.0 ml 20% aqueous ammonia solution drops 20-Volume aqueous hydrogen peroxide solution 1.0 ml
[0162] The oxidation bases tested are the following: [0163] B2 is 1-[3-(2,5-diaminophenyl)propyl]-3-methyl-1H-imidazol-3-ium chloride dihydrochloride (Invention) [0164] D2 is 1-[2-(2,5-diaminophenyl)ethyl]-3-methyl-1 H-imidazol-3-ium chloride dihydrochloride (Comparative composition)
[0165] The oxidation couplers tested are the following: [0166] C1 is 3,4-dihydro-2H-1,4-benzoxazin-6-ol [0167] C5 is resorcinol [0168] C6 is 2-methylbenzene-1,3-diol [0169] C7 is 2-(2,4-diaminophenoxy)ethanol dihydrochloride [0170] C8 is 1H-indol-6-ol
[0171] Each composition is applied to a 0.5 g lock of natural Caucasian hair comprising 90% white hairs. After a leave-on time of 30 minutes at ambient temperature, the locks are rinsed with water, washed with a standard shampoo, rinsed again and then dried. The colorimetric data for each of the locks are then measured with a Minolta CM-3610d spectrophotometer.
[0172] Evaluation of the Intensity L* of the Dyes
TABLE-US-00009 Ox. bases D2 (comparative Couplers B2 (invention) composition) C5 41.59 43.03 C6 43.64 45.16 C7 20.53 22.13 C8 34.83 44.09
[0173] Evaluation of the Buildup ΔE of the Dyes
TABLE-US-00010 Ox. bases D2 (comparative Couplers B2 (invention) composition) C1 14.43 12.75 C6 10.07 8.69 C8 16.6 14.74
[0174] It is apparent from the above results that the dyeing method according to the invention which uses bases of cationic heterocyclic para-phenylenediamine type with a propylene chain vs a dyeing method which does not use a base of cationic heterocyclic para-phenylenediamine type with an ethylene chain, that the colorings obtained with the method of the invention are more intense than the comparative composition, and the buildup according to the invention is greater than that obtained with the comparative composition.
Example 4
Evaluation of the Intensity, the Buildup and the Shampoo Resistance of the Dyes vs. Other Comparative Composition
[0175] Composition (A) according to the present invention was prepared from the ingredients, the contents of which are indicated, as weight percentage of active material relative to the total weight of composition, in the table below:
TABLE-US-00011 Ingredients Composition A 96° ethyl alcohol 20.8 35% aqueous sodium metabisulfite solution 0.23 40% aqueous solution of the pentasodium salt of 0.48 diethylenetriaminepentaacetic acid 60% aqueous solution of C.sub.8-C.sub.10 alkyl polyglucoside 3.6 Benzyl alcohol 2.0 Polyethylene glycol containing 8 ethylene oxide 3.0 units NH.sub.4Cl 4.32 Aqueous ammonia containing 20% NH.sub.3 2.94 Compound of formula (I) 10.sup.−3 mol Oxidation coupler 10.sup.−3 mol Water qs 100
[0176] At the time of use, each of the compositions is mixed with a 20-volume (6% by weight) aqueous hydrogen peroxide solution in a 1:1 ratio. The final pH of each of the mixtures is equal to 9.5. Each mixture thus obtained is applied to a lock of gray hair containing 90% white hairs. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo and then rinsed again. The locks are then dried.
[0177] The shampoo resistance of the color on the hair corresponds to the difference in color buildup before and after shampooing (˜50% DOP shampoo, 6 cycles of 1 shampoo wash +3 rinses, on a transparent Pall plate) or (˜2% DOP shampoo, 6 shampoo washes).
[0178] The light fastness of the color on the hair corresponds to the value of the difference in color buildup before and after exposure to light (Xenon-1600W, exposure 2 h 26 min, ˜1 month of normal life).
[0179] The compounds of formula (I) (oxidation bases) are numbered as follows: [0180] B2 is 1-[3-(2,5-diaminophenyl)propyl]-3-methyl-1H-imidazol-3-ium chloride dihydrochloride (Invention) [0181] B3 is 1-[3-(2,5-diaminophenyl)propyl]-2-methyl-1 H-pyrazol-2-ium chloride dihydrochloride (Invention) [0182] B4 is 4-[3-(2,5-diaminophenyl)propyl]-4-methylthiomorpholin-4-ium chloride dihydrochloride (Invention) [0183] D2′ is 2-[3-(1H-imidazol-1-yl)propyl]benzene-1,4-diamine chloride dihydrochloride (Comparative composition) [0184] D3 is 2-[3-(1H-pyrazol-1-yl)propyl]benzene-1,4-diamine chloride dihydrochloride (Comparative composition) [0185] D4 is 2-[3-(thiomorpholin-4-yl)propyl]benzene-1,4-diamine chloride dihydrochloride (Comparative composition)
[0186] The oxidation couplers are numbered as follows: [0187] C2 is 5-[(2-hydroxyethyl)amino]-2-methylphenol [0188] C3 is 2-aminopyridin-3-ol [0189] C4 is 3-amino-2-chloro-6-methylphenol [0190] C5 is resorcinol [0191] C6 is 2-methylbenzene-1,3-diol [0192] C8 is 1 H-indol-6-ol [0193] C9 is 5-amino-2-methylphenol [0194] 010 is 2-(2,4-diaminophenoxy)ethanol hydrochloride
[0195] Evaluation of the Intensity of the Dyes: L*
TABLE-US-00012 Bases D2′ (comparative Couplers B2 (invention) composition) C2 28.05 31.04 C4 23.30 26.66 C6 31.8 34.7 C9 24.43 30.57
[0196] It was observed visually that the keratin fibers treated with the cationic oxidation bases according to the invention make it possible to improve the intensity of the color of the fibers vs. the color obtained with the non-cationic comparative oxidation bases. This was corroborated with the results of the above table of L* measured which shows significant differences in improvement of the intensity for various couplers.
[0197] Evaluation of the Buildup of the Dyes ΔE
TABLE-US-00013 Bases D2′ (comparative Couplers B2 (invention) composition) C2 18.81 15.57 C4 25.01 21.91 C6 11.24 8.43 C9 21.94 16.77
[0198] A much better color buildup was also observed for the cationic oxidation bases of the invention than for the comparative non-cationic oxidation bases. This observation is corroborated with the table of ΔE calculated from the values of L, a, b measured above.
[0199] Evaluation of the Shampoo Resistance of the Dyes
TABLE-US-00014 Bases D2′ comparative Couplers B2 invention composition C3 1.42 4.60 C10 3.86 6.29
TABLE-US-00015 Bases D4 comparative Couplers B4 invention composition C3 1.75 4.57 C5 0.95 2.26 C8 1.38 3.19
[0200] It is apparent from the above results that the dyeing method according to the invention which uses bases of cationic heterocyclic para-phenylenediamine type vs. a dyeing method which uses a base of non-cationic heterocyclic para-phenylenediamine type, makes it possible to obtain colorations which are significantly more shampoo-resistant than that obtained with the comparative compositions.