WO2002039970A1 - Novel coupler for use in oxidative hair dyeing - Google Patents

Novel coupler for use in oxidative hair dyeing Download PDF

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Publication number
WO2002039970A1
WO2002039970A1 PCT/US2001/043867 US0143867W WO0239970A1 WO 2002039970 A1 WO2002039970 A1 WO 2002039970A1 US 0143867 W US0143867 W US 0143867W WO 0239970 A1 WO0239970 A1 WO 0239970A1
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WIPO (PCT)
Prior art keywords
amino
methyl
phenol
group
hair
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PCT/US2001/043867
Other languages
French (fr)
Inventor
Mu-Ill Lim
Yuh-Guo Pan
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P&G - Clairol, Inc.
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Publication date
Application filed by P&G - Clairol, Inc. filed Critical P&G - Clairol, Inc.
Priority to EP01996355A priority Critical patent/EP1333795A4/en
Priority to AU1983502A priority patent/AU1983502A/en
Priority to JP2002542345A priority patent/JP2004513910A/en
Priority to MXPA03004379A priority patent/MXPA03004379A/en
Priority to AU2002219835A priority patent/AU2002219835B2/en
Priority to CA002424965A priority patent/CA2424965C/en
Publication of WO2002039970A1 publication Critical patent/WO2002039970A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/416—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • This invention relates to novel couplers for use in hair coloring compositions comprising one or more oxidative hair coloring agents in combination with one or more oxidizing agents.
  • the invention also relates to hair coloring compositions of these novel couplers and to coloring or dyeing of hair using compositions containing these couplers.
  • Coloration of hair is a procedure practiced from antiquity employing a variety of means.
  • the most extensively used method employed to color hair is to color hair by an oxidative dyeing process employing hair coloring systems utilizing one or more oxidative hair coloring agents in combination with one or more oxidizing agents.
  • a peroxy oxidizing agent is used in combination with one or more oxidative hair coloring agents, generally small molecules capable of diffusing into hair and comprising one or more primary intermediates and one or more couplers.
  • a peroxide material such as hydrogen peroxide, is employed to activate the small molecules of primary intermediates so that they react with couplers to form larger sized compounds in the hair shaft to color the hair in a variety of shades and colors.
  • a wide variety of primary intermediates and couplers have been employed in such oxidative hair coloring systems and compositions.
  • the primary intermediates employed there may be mentioned p-phenylenediamine, p- toluenediamine, p-aminophenol, 4-amino-3-methylphenol, and as couplers there may be mentioned resorcinol, 2-methylresorcinol, 3-aminophenol, and 5-amino-2-methylphenol.
  • couplers there may be mentioned resorcinol, 2-methylresorcinol, 3-aminophenol, and 5-amino-2-methylphenol.
  • a majority of the shades have been produced with dyes based on p-phenylenediamine.
  • This invention provides novel couplers of the formula (1 ):
  • X is selected from halogen where the halogen is preferably CI, Br or I;
  • R 3 is selected from Ci to C 2 alkyl and hydroxyethyl;
  • R, R 1 and R 2 are each independently selected from C-i to C 22 alkyl or Ci to C 22 mono or dihydroxyalkyl groups or two of R, R 1 and R 2 together with the nitrogen atom to which they are attached form a C 3 to C ⁇ cycloaliphatic or a C 3 to C aromatic group, the cycloaliphatic or aromatic group optionally containing in their rings one or more hetero atoms selected from O, S and N atoms.
  • novel couplers are used to provide coloration to hair in which there is good dye uptake by the hair and provides shades or colors which are stable over a relatively long period of time.
  • the novel couplers provide for dyeing of hair that provides color or shades that possess good wash fastness and do not undergo the significant changes on exposure to light or shampooing as experienced with 2-methyl-5-aminophenol.
  • Preferred coupler compounds of this invention are those of formula (1)
  • X is CI, Br or I; R 3 is methyl, ethyl or hydroxyethyl; and two of R, R 1 and R 2 together with the nitrogen atom to which they are attached form an C 3 to C ⁇ cycloaliphatic or C 3 to CQ aromatic group optionally containing in the ring another N atom.
  • Especially preferred couplers of this invention are the following compounds: 1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride; 1-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride; 1-[2-(3-hydroxy-4-hydroxyethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride;
  • Hair coloring compositions of this invention can contain the novel couplers of this invention as the sole coupler or can also contain other couplers in combination with primary intermediates.
  • Suitable primary intermediates include, for example,
  • p-phenylenediamine derivatives such as: benzene-1 ,4-diamine
  • p-aminophenol derivatives such as: 4-amino-phenol (commonly known as p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyi-phenol, 4-amino-2- hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-[(2-hydroxy-ethylamino)- methyl]-phenol, 4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid, 1-(5-amino-2-hydroxy-phenyl)-ethane-1 ,2-diol, 4-amino-2-(2-hydroxy-ethyl)-phenol, 4- amino-3-(hydroxymethyl)phenol, 4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)- phenol, and 4-amino-2-fluoro-phenol;
  • o-aminophenol derivatives such as: 2-amino-phenol (commonly known as o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl- phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; and heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonly known as 2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole-4,5-diamine, 2-(4,5-diamino-1 H-pyrazol-1-yl)ethanol, N 2 ,N 2 -dimethyl-pyridine-2,5-diamine, 2-[(3- amino-6-methoxypyridin-2-yl)amino]ethanol, 6-methoxy-N 2 -methyl-pyridine-2,3- diamine, 2,5,6-triaminopyrimidin-4
  • couplers of formula (1 ) of this invention may be used with any suitable coupler(s) in hair coloring compositions or systems of this invention.
  • Suitable known couplers include, for example:
  • phenols, resorcinol and naphthol derivatives such as: naphthalene-1 ,7- diol, benzene-1 ,3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl- naphthalen-1-ol, naphthalene-1 ,5-diol, naphthalene-2,7-diol, benzene-1 ,4-diol, 2- methyl-benzene-1 ,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonic acid, 2-isopropyl- 5-methylphenol, 1 ,2,3,4-tetrahydro-naphthalene-1 ,5-diol, 2-chloro-benzene-1 ,3-diol, 4- hydroxy-naphthalene-1-sulfonic acid, benzene-1 ,
  • m-phenylenediamines such as: 2,4-diaminophenol, benzene-1 ,3- diamine, 2-(2,4-diamino-phenoxy)-ethanol, 2-[(3-amino-phenyl)-(2-hydroxy-ethyl)- amino]-ethanol, 2-mehyl-benzene-1 ,3-diamine, 2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2- hydroxy-ethyl)-amino]-ethanol, 4- ⁇ 3-[(2,4-diaminophenyl)oxy]propoxy ⁇ benzene-1 ,3- diamine, 2-(2,4-diamino-phenyl)-ethanol, 2-(3-amino-4-methoxy-phenylamino)- ethanol, 4-(2-amino-ethoxy)-benzene-1 ,3-diamine, (2,4-diamino-phenoxy)-
  • m-aminophenols such as: 3-amino-phenol, 2-(3-hydroxy-4-methyl- phenylamino)-acetamide, 2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl- phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol, 3- amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 5-amino-2-(2-hydroxy- ethoxy)-phenol, 2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol, 5-amino-4-chloro-2- methyl-phenol, 3-cyclopentylamino-phenol, 5-[(2-hydroxyethyl)amino]-4-methoxy-2- methylphenol, 5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol, 3- (diethylamino)phenol,
  • heterocyclic derivatives such as: 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol, 4- methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 6-methoxyquinolin-8-amine, 4- methylpyridine-2,6-diol, 2,3-dihydro-1 ,4-benzodioxin-5-ol, 1 ,3-benzodioxol-5-ol, 2-(1 ,3- benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol, 5-chloropyridine-2,3- diol, 2,6-dimethoxypyridine-3,5-diamine, 1 ,3-benzodioxol-5-amine, 2- ⁇ [3,5-diamino-6- (2-hydroxy-ethoxy)-pyridin-2-yl]oxy ⁇ -ethanol, 1 H-indo
  • Preferred primary intermediates include:
  • p-phenylenediamine derivatives such as: 2-methyl-benzene-1 ,4-diamine, benzene-1 ,4-diamine, 1 -(2,5-diamino-phenyl)-ethanol, 2-(2,5-diamino-phenyl)-ethanol, N-(2-methoxyethyl)benzene-1 ,4-diamine, 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)- amino]-ethanol, and 1 -(2, 5-diaminophenyl)ethane-1 ,2-diol;
  • p-aminophenol derivatives such as 4-amino-phenol, 4-methylamino- phenol, 4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol, and 1-(5-amino- 2-hydroxy-phenyl)-ethane-1 ,2-diol;
  • o-aminophenol derivatives such as: 2-amino-phenol, 2-amino-5-methyl- phenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2- amino-4-methyl-phenol;
  • heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine, 1-methyl-
  • Preferred couplers include:
  • phenols, resorcinol and naphthol derivatives such as: naphthalene-1 ,7- diol, benzene-1 ,3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl-naphthalen- 1-ol, naphthalene-1 ,5-dioI, naphthalene-2,7-diol, benzene-1 ,4-diol, 2-methyl-benzene- 1 ,3-diol, and 2-isopropyl-5-methylphenol; m-phenylenediamines such as: benzene-1 ,3-diamine, 2-(2,4-diamino- phenoxy)-ethanol, 4- ⁇ 3-[(2,4-diaminophenyl)oxy]propoxy ⁇ benzene-1 ,3-diamine , 2-(3- amino-4-methoxy-phen
  • m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol, 5- (2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol; and
  • heterocyclic derivatives such as: 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol, 4- methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1 ,3-benzodioxol-5-ol, 1 ,3-benzodioxol- 5-amine, 1 H-indol-4-ol, 1 H-indole-5,6-diol, 1 H-indol-7-ol, 1 H-indol-5-ol, 1 H-indol-6-ol, 1 H-indole-2,3-dione, pyridine-2,6-diamine,and 2-aminopyridin-3-ol.
  • Most preferred primary intermediates include:
  • p-phenylenediamine derivatives such as: 2-methyl-benzene-1 ,4-diamine, benzene-1 ,4-diamine, 2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)- ethanol, and 2-[(4-amino-phenyI)-(2-hydroxy-ethyl)-amino]-ethanol;
  • p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino- phenol, 4-amino-3-methyl-phenol, and 1-(5-amino-2-hydroxy-phenyl)-ethane-1 ,2-diol;
  • o-aminophenols such as: 2-amino-phenol, 2-amino-5-methyl-phenol, 2- amino-6-methyI-phenol, and N-(4-amino-3-hydroxy-phenyl)-acetamide; and
  • heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine, 2-(4,5- diamino-1H-pyrazol-1-yl)ethanol, 1-(4-methyIbenzyl)-1 H-pyrazole-4,5-diamine, and 1- (benzyl)-1 H-pyrazole-4,5-diamine.
  • Most preferred couplers include:
  • phenols, resorcinol and naphthol derivatives such as: benzene-1 ,3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol, and 2-methyl- benzene-1 ,3-diol;
  • m-phenylenediamine such as: 2-(2,4-diamino-phenoxy)-ethanol, 2-(3- amino-4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)- phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol;
  • m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol, 5- (2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol; and
  • heterocyclic derivatives such as: 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol, 4- methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1 H-indol-6-ol, and 2-aminopyridin-3-ol.
  • the coupler compounds and the primary intermediate compounds, as well as the other dye compounds, in so far as they are bases can be used as free bases or in the form of their physiologically compatible salts with organic or inorganic acids, such as hydrochloric acid or sulfuric acid, or, in so far as they have aromatic OH groups, in the form of their salts with bases, such as alkali phenolates.
  • the total amount of the combination of dye precursors (e.g., primary intermediate and coupler compounds) in the hair coloring compositions or systems of this invention is generally from about 0.001 to about 10, preferably from about 0.02 to about 10, and most preferably from about 0.2 to about 6.0 weight percent based on the total weight of the hair coloring composition.
  • the primary intermediate and coupler compounds are generally used in equivalent amounts. However, it is possible to use the primary intermediate compounds in either excess or deficiency, i.e., a molar ratio of primary intermediate to coupler generally ranging from about 5:1 to about 1 :5.
  • the hair coloring compositions of this invention will contain the couplers of this invention in an effective coloring amount, generally in an amount of from about 0.001 to about 6 weight percent by weight of the hair dye composition, preferably from about 0.01 to about 3.5 weight percent.
  • Other couplers, when present, are typically present in an amount such that in aggregate the concentration of couplers in the composition is from about 0.01 to about 6 weight percent.
  • the primary intermediate(s) is present in an effective dyeing concentration generally an amount of from about 0.001 to about 6.0 weight percent by weight of the hair dye composition, preferably from about 0.01 to about 3.5 weight percent.
  • Any suitable carrier or vehicle generally an aqueous or hydroalcoholic solution, can be employed, preferably an aqueous solution.
  • the carrier or vehicle will generally comprise up to about 40 weight percent.
  • the hair coloring compositions of this invention may contain one or more cationic, anionic or amphoteric surface active agents, perfumes, antioxidants, sequestering agents, thickening agents, alkalizing or acidifying agents, and other dyeing agents.
  • compositions of the present invention are used by admixing them with a suitable oxidant, which reacts with the hair dye precursors to develop the hair dye.
  • a suitable oxidant which reacts with the hair dye precursors to develop the hair dye.
  • Any suitable peroxide providing agent can be employed in the coloring compositions of this invention, particularly hydrogen peroxide (H 2 O 2 ) or precursors therefor.
  • H 2 O 2 hydrogen peroxide
  • urea peroxide sodium perborate, sodium percarbonate, and melamine peroxide.
  • cosmetic additive ingredients which are commonly used in compositions for coloring hair, can be used in the hair coloring compositions according to the invention, for example antioxidants, such as ascorbic acid, thioglycolic acid or sodium sulfite, and perfume oils, complex formers, wetting agents, emulsifiers, thickeners and care materials.
  • antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite
  • perfume oils complex formers, wetting agents, emulsifiers, thickeners and care materials.
  • the form of the hair coloring compositions according to the invention can be, for example, a solution, especially an aqueous or aqueous-alcoholic solution.
  • a solution especially an aqueous or aqueous-alcoholic solution.
  • the form that is particularly preferred is a cream, gel or an emulsion.
  • Its composition is a mixture of the dye ingredients with the conventional cosmetic additive ingredients suitable for the particular preparation.
  • Conventional cosmetic additive ingredients in solutions, creams, emulsion or gels include, for example:
  • solvents In addition to water, solvents that can be used are lower alkanols (e.g.,ethanol, propanol, isopropanol); polyols (e.g., carbitols, propylene glycol, glycerin). Under suitable processing, higher alcohols, such as cetyl alcohol, are suitable organic solvents, provided they are first liquified by melting, typically at low temperature (50 to 80 °C), before incorporation of other, usually lipophilic, materials. See WO 98/27941 (section on diluents) incorporated by reference.
  • Anionic and Nonionic Surfactants are from the classes of anionic, cationic, amphoteric or nonionic surfactant compounds, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzensulfonat.es, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanol amides and ethoxylated fatty acid esters.
  • anionic, cationic, amphoteric or nonionic surfactant compounds such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzensulfonat.es, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated non
  • Suitable materials are alkyl sulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, acyl isethionates, alkyl ethoxy carboxylates, fatty acid mono- and diethanolamides.
  • WO 98/52523 published November 26, 1998 and incorporated herein by reference.
  • Suitable thickeners include such as higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oil, fatty acids and anionic and nonionic polymeric thickeners based on polyacrylic and polyurethane polymers. Examples are hydroxyethyl cellulose, hydroxymethylcellulose and other cellulose derivatives, hydrophobically modified anionic polymers and nonionic polymers, particularly such polymers having both hydrophilic and hydrophobic moieties (i.e., amphiphilic polymers).
  • Useful nonionic polymers include polyurethane derivatives such as PEG- 150/stearyl alcohol/SDMI copolymer and PEG-150/stearyl alcohol SDMI copolymer.
  • amphiphilic polymers are disclosed in US Pat. No. 6010541 incorporated by reference.
  • anionic polymers that can be used as thickeners are acrylates copolymer, acrylates/ceteth-20 methacrylates copolymer, acrylates/ceteth- 20 itaconate copolymer, and acrylates/beheneth-25 acrylates copolymer.
  • Alkalizing agents Suitable materials that are used to increase pH of the hair dye compositions include ammonia, aminomethylpropanol, methylethanolamine, triethanolamine and ethanolamine.
  • Suitable materials include silicones and silicone derivatives; hydrocarbon oils; monomeric quaternary compounds, and quaternized polymers.
  • Monomeric quaternary compounds are typically cationic compounds, but may also include betaines and other amphoteric and zwitterionic materials.
  • Suitable monomeric quaternary compounds include behentrialkonium chloride, behentrimonium chloride, benzalkonium bromide or chloride, benzyl triethyl ammonium chloride, bis-hydroxyethyl tallowmonium chloride, C12-18 dialkyldimonium chloride, cetalkonium chloride, ceteartrimonium bromide and chloride, cetrimonium bromide, chloride and methosulfate, cetylpyridonium chloride, cocamidoproypl ethyldimonium ethosulfate, cocamidopropyl ethosulfate, coco-ethyldimonium ethosulfate, cocotrimonium chloride and ethosulfate, dibehenyl dimonium chloride, dicetyldimonium chloride, dicocodimonium chloride, dilauryl dimonium chloride, disoydimonium chloride, ditallowdimonium
  • Quatemized polymers are typically cationic polymers, but may also include amphoteric and zwitterionic polymers.
  • Useful polymers are exemplified by polyquatemium-4, polyquaternium-6, polyquaternium-7, polyquatemium-8, polyquatemium-9, polyquaternium-10, polyquaternium-22, polyquaternium-32, polyquaternium-39, polyquaternium-44 and polyquatemium-47.
  • Silicones suitable to condition hair are dimethicone, amodimethicone, dimethicone copolyol and dimethiconol. See also WO 99/34770 published July 15,1999, incorporated by reference, for suitable silicones.
  • Suitable hydrocarbon oils would include mineral oil.
  • Natural ingredients For example, protein derivatives, aloe, camomile and henna extracts.
  • adjuvants include acidulents to lower pH, buffers, chelating agents antioxidants, sequestrants, etc.
  • These classes of materials and other species of materials in the classes referred to above but not specifically identified that are suitable are listed in the International Cosmetics Ingredient Dictionary and Handbook, (Eighth Edition) published by The Cosmetics, Toiletry, and Fragrance Association, incorporated by reference. In particular reference is made to Volume 2, Section 3 (Chemical Classes) and Section 4 (Functions) are useful in identifying a specific adjuvant/excipient to achieve a particular purpose or multipurpose.
  • the above-mentioned conventional cosmetic ingredients are used in amounts suitable for their purposes.
  • the wetting agents and emulsifiers are used in concentrations of from about 0.5 to 30 percent by weight
  • the thickeners are used in an amount of from about 0.1 to 25 percent by weight
  • the hair care materials are used in concentrations of from about 0.1 to 5.0 percent by weight.
  • the hair coloring compositions according to the invention can be weakly acidic, neutral or alkaline according to their composition.
  • the compositions typically have pH values of from 6.8 to 11.5. Their pH can be adjusted in the basic range with ammonia.
  • organic amines can be used for this purpose, including monoethanolamine and triethanolamine, or also inorganic bases, such as sodium hydroxide and potassium hydroxide.
  • Inorganic or organic acids can be used for adjusting the pH in the acid range, for example phosphoric acid, acetic acid, citric acid or tartaric acid.
  • the hair coloring compositions of this invention will contain the couplers of this invention, alone or in combination with other couplers, in an effective coloring amount, generally in an amount of from about 0.01 to about 2.5 weight percent. Other couplers, when present will be present in an amount up to about 2.5 weight percent.
  • the primary intermediate(s) will generally be present in an amount of from about 0.01 to about 3.5 weight percent.
  • the molar ratio of primary intermediate to coupler will generally range from about 5:1 to about 1 :5 and be employed in any suitable carrier or vehicle, generally an aqueous or hydroalcoholic solution, preferably an aqueous solution.
  • the carrier or vehicle will generally comprise up to about 40 weight percent.
  • the oxidation hair coloring composition for dyeing hair one mixes the above-described hair coloring compositions according to the invention with an oxidizing agent immediately prior to use and applies a sufficient amount of the mixture to the hair, according to the hair abundance, generally from about 60 to 200 grams.
  • Some of the adjuvants listed above e.g., thickeners, conditoners, etc.
  • hydrogen peroxide, or its addition compounds with urea, melamine, sodium borate or sodium carbonate can be used in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution as the oxidizing agent for developing the hair dye.
  • Oxygen can also be used as the oxidizing agent. If a 6 percent hydrogen peroxide solution is used as oxidizing agent, the weight ratio of hair coloring composition and oxidizing agent is 5:1 to 1:2, but preferably 1 :1.
  • the mixture of the oxidizing agent and the dye composition of the invention is allowed to act on the hair for about 10 to about 45 minutes, preferably about 30 minutes, at about 15 to 50°C, the hair is rinsed with water and dried. If necessary, it is washed with a shampoo and eventually after-rinsed with a weak organic acid, such as citric acid or tartaric acid. Subsequently the hair is dried.
  • the hair coloring composition according to the invention with a compound of formula (1) of this invention as coupler substances permits hair dyeing with outstanding color fastness, especially light fastness, fastness to washing and fastness to rubbing.
  • a first composition of primary intermediate(s) and coupler(s) is prepared and then, at the time of use, the oxidizing agents, such as H 2 O 2 , is admixed therewith until an essentially homogenous composition is obtained which is applied to the hair to be dyed and permitted to remain in contact with the hair for a dyeing effective amount of time, generally for a period of from about 2 to 45, preferably about 2 to 30, minutes, after which the hair is rinsed, shampooed and dried.
  • a separate conditioning product may also be provided.
  • the hair dye composition of the present invention comprising the hair dye coupler (1 ) and the developer comprising the oxidizing agent form a system for dyeing hair.
  • This system may be provided as a kit comprising in a single package separate containers of the hair dye compositions, the developer, the optional conditioner or the hair treatment product, and instructions for use.
  • compositions shown in Table 1 can be used for dyeing Piedmont hair.
  • the dyeing solution is mixed with 100 g 20 volume hydrogen peroxide.
  • the resulting mixture is applied to the hair and permitted to remain in contact with the hair for 30 minutes.
  • This dyed hair is then shampooed and rinsed with water and dried
  • these ingredients are in the range of 2 to 15% by weight.
  • At least one of these dye precursors is typically present.
  • Exemplary combinations of hair coloring components employing a coupler compound of formula (1) of this invention are show in combinations in Table 1 and in C1 to C126 in Table A. Reading down the columns in Table A, the Xes designate the dye compounds (including the novel couplers of the instant invention) that form illustratively suitable combinations of dyes that can be formulated according to the present invention.
  • the novel couplers of the present invention (Row 1 of Table A) with X, R, R 1 , R 2 and R 3 are as defined hereinbefore, can be combined with p-toluene diamine and 2-amino-phenol.
  • the couplers of formula (1) of this invention in the combinations C1 to C126 of Table A are:

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Abstract

Couplers for hair coloring compositions for oxidative dyeing of hair are compounds of formula (1): wherein X is selected from halogen; R3 is selected from the group consisting of C?1 and C2¿ alkyl and hydroxyethyl; and R and R?1 and R2 ¿are each independently selected from C?1 to C22¿ alkyl or C?1 to C22¿ mono or dialkyl groups, or two of R, R?1 and R2¿ together with the nitrogen atom which they are attached form a C3 to C6 cycloaliphatic or a C?3 to C14¿ aromatic group, the cycloaliphatic or aromatic group optionally containing in their rings one or more hetero atoms selected from O, S and N atoms.

Description

NOVEL COUPLER FOR USE IN OXIDATIVE HAIR DYEING
Field of the Invention
This invention relates to novel couplers for use in hair coloring compositions comprising one or more oxidative hair coloring agents in combination with one or more oxidizing agents. The invention also relates to hair coloring compositions of these novel couplers and to coloring or dyeing of hair using compositions containing these couplers.
Background of the Invention
Coloration of hair is a procedure practiced from antiquity employing a variety of means. In modern times, the most extensively used method employed to color hair is to color hair by an oxidative dyeing process employing hair coloring systems utilizing one or more oxidative hair coloring agents in combination with one or more oxidizing agents.
Most commonly a peroxy oxidizing agent is used in combination with one or more oxidative hair coloring agents, generally small molecules capable of diffusing into hair and comprising one or more primary intermediates and one or more couplers. In this procedure, a peroxide material, such as hydrogen peroxide, is employed to activate the small molecules of primary intermediates so that they react with couplers to form larger sized compounds in the hair shaft to color the hair in a variety of shades and colors.
A wide variety of primary intermediates and couplers have been employed in such oxidative hair coloring systems and compositions. Among the primary intermediates employed there may be mentioned p-phenylenediamine, p- toluenediamine, p-aminophenol, 4-amino-3-methylphenol, and as couplers there may be mentioned resorcinol, 2-methylresorcinol, 3-aminophenol, and 5-amino-2-methylphenol. A majority of the shades have been produced with dyes based on p-phenylenediamine.
For providing an orange coloration to hair 2-methyl-5-aminophenol has been extensively used in combination with p-aminophenol as a primary intermediate. However, the resulting orange color on hair undergoes significant changes on exposure to light or shampooing. US Patent No. 4,065,255 and EP patent publications EP 634165 A1 and EP 667143 A1 suggest the use of 2-methyl-5-N- hydroxyethylaminophenol, 2-methyl-5-alkylaminophenol and 2-methyl-5-aminophenol as couplers. Therefore, there is a need for new orange couplers for use in oxidative hair dyeing compositions and systems.
Brief Summary of the Invention
This invention provides novel couplers of the formula (1 ):
Figure imgf000003_0001
d) wherein X is selected from halogen where the halogen is preferably CI, Br or I; R3 is selected from Ci to C2 alkyl and hydroxyethyl; and R, R1 and R2 are each independently selected from C-i to C22 alkyl or Ci to C22 mono or dihydroxyalkyl groups or two of R, R1 and R2 together with the nitrogen atom to which they are attached form a C3 to Cβ cycloaliphatic or a C3 to C aromatic group, the cycloaliphatic or aromatic group optionally containing in their rings one or more hetero atoms selected from O, S and N atoms. These novel couplers are used to provide coloration to hair in which there is good dye uptake by the hair and provides shades or colors which are stable over a relatively long period of time. The novel couplers provide for dyeing of hair that provides color or shades that possess good wash fastness and do not undergo the significant changes on exposure to light or shampooing as experienced with 2-methyl-5-aminophenol.
Detailed Description of the Invention
Preferred coupler compounds of this invention are those of formula (1)
Figure imgf000004_0001
d)
wherein X is CI, Br or I; R3 is methyl, ethyl or hydroxyethyl; and two of R, R1 and R2 together with the nitrogen atom to which they are attached form an C3 to Cβ cycloaliphatic or C3 to CQ aromatic group optionally containing in the ring another N atom.
Especially preferred couplers of this invention are the following compounds: 1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride; 1-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride; 1-[2-(3-hydroxy-4-hydroxyethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride;
1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium bromide; 1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium iodide;
1-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium propyl sulfate;
N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-pipehdinium chloride; N-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl-N'-methyl-piperidinium chloride; N-[2-(3-hydroxy-4-hydroxyethyl-phenylamino)-ethyl-N'-methyl-piperidinium chloride;
N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-piperidinium bromide;and N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-piperidinium iodide.
The compounds of formula (1 ) of this invention are readily prepared according to the following reaction sequence.
Figure imgf000006_0001
(6)
(5)
Figure imgf000006_0002
(1 )
In the reaction sequence a solution of an aminophenol of formula (2) in tetrahydrofuran (THF) is added to a solution of haloacetyl chloride to produce a compound of formula (5). Treatment of the compound of formula (5) with a borane- THF complex produces a compound of formula (6) and reaction of this compound of formula (6) with a quaternization reagent of the formula N(R1)(R2)(R3) produces a compound of formula (1). Synthesis Examples 1-10
Employing the appropriate aminophenol, haloacetylchloride, and
N(R1)(R2)(R3) quaternization reagent in the forgoing described synthesis procedure the following coupler compounds of this invention are prepared.
1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride;
N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-piperidinium chloride;
1-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride;
1-[2-(3-hydroxy-4-hydroxyethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride;
1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium bromide;
1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium iodide;
N-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl-N'-methyl-piperidinium chloride;
N-[2-(3-hydroxy-4-hydroxyethyl-phenylamino)-ethyl-N'-methyl-piperidinium chloride; N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-piperidinium bromide; and
N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-piperidinium iodide.
Hair coloring compositions of this invention can contain the novel couplers of this invention as the sole coupler or can also contain other couplers in combination with primary intermediates.
For hair coloring compositions of this invention, there may be used one or more suitable primary intermediates in combination with the novel couplers of this invention. Suitable primary intermediates include, for example,
p-phenylenediamine derivatives such as: benzene-1 ,4-diamine
(commonly known as p-phenylenediamine), 2-methyl-benzene-1 ,4-diamine, 2-chloro- benzene-1 ,4-diamine, N-phenyl-benzene-1 ,4-diamine, N-(2-ethoxyethyl)benzene-1 ,4- diamine, 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known as N,N-bis(2-hydroxyethyl)-p-phenylenediamine) (2,5-diamino-phenyl)-methanol, 1 -(2,5- diamino-phenyl)-ethanol, 2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene- 1 ,4-diamine, 2,6-dimethyl-benzene-1 ,4-diamine, 2-isopropyl-benzene-1 ,4-diamine, 1- [(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1 ,4-diamine, 1 ,3-bis[(4- aminophenyl)(2-hydroxyethyl)amino]propan-2-ol, N4,N4,2-trimethylbenzene-1 ,4- diamine, 2-methoxy-benzene-1 ,4-diamine, 1-(2,5-diaminophenyl)ethane-1 ,2-diol, 2,3- dimethyl-benzene-1 ,4-diamine, N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6- diethylbenzene-1 ,4-diamine, 2,5-dimethylbenzene-1 ,4-diamine, 2-thien-2-ylbenzene- 1 ,4-diamine, 2-thien-3-ylbenzene-1 ,4-diamine, 2-pyridin-3-ylbenzene-1 ,4-diamine, 1 ,1'-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1 ,4-diamine, 2-
(aminomethyl)benzene-l ,4-diamine, 2-(2,5-diaminophenoxy)ethanol, N-[2-(2,5- diaminophenoxy)ethyl]-acetamide, N,N-dimethylbenzene-1 ,4-diamine, N,N- diethylbenzene-1 ,4-diamine, N,N-dipropylbenzene-1 ,4-diamine, 2-[(4- aminophenyl)(ethyl)amino]ethanol, 2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)- amino]-ethanol, N-(2-methoxyethyl)-benzene-1 ,4-diamine, 3-[(4- aminophenyl)amino]propan-1-ol, 3-[(4-aminophenyl)-amino]propane-1 ,2-diol, N-{4-[(4- aminophenyl)amino]butyl}benzene-1 ,4-diamine, and 2-[2-(2-{2-[(2,5-diaminophenyl)- oxy]ethoxy}ethoxy)ethoxy]benzene-1 ,4-diamine;
p-aminophenol derivatives such as: 4-amino-phenol (commonly known as p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyi-phenol, 4-amino-2- hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-[(2-hydroxy-ethylamino)- methyl]-phenol, 4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid, 1-(5-amino-2-hydroxy-phenyl)-ethane-1 ,2-diol, 4-amino-2-(2-hydroxy-ethyl)-phenol, 4- amino-3-(hydroxymethyl)phenol, 4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)- phenol, and 4-amino-2-fluoro-phenol;
o-aminophenol derivatives such as: 2-amino-phenol (commonly known as o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl- phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; and heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonly known as 2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole-4,5-diamine, 2-(4,5-diamino-1 H-pyrazol-1-yl)ethanol, N2,N2-dimethyl-pyridine-2,5-diamine, 2-[(3- amino-6-methoxypyridin-2-yl)amino]ethanol, 6-methoxy-N2-methyl-pyridine-2,3- diamine, 2,5,6-triaminopyrimidin-4(1 H)-one, pyridine-2,5-diamine, 1-isopropyl-1 H- pyrazole-4,5-diamine, 1 -(4-methylbenzyl)-1 H-pyrazole-4,5-diamine, 1 -(benzyl)-1 H- pyrazole-4,5-diamine and 1-(4-chlorobenzyl)-1 H-pyrazole-4,5-diamine.
The couplers of formula (1 ) of this invention may be used with any suitable coupler(s) in hair coloring compositions or systems of this invention.
Suitable known couplers include, for example:
phenols, resorcinol and naphthol derivatives such as: naphthalene-1 ,7- diol, benzene-1 ,3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl- naphthalen-1-ol, naphthalene-1 ,5-diol, naphthalene-2,7-diol, benzene-1 ,4-diol, 2- methyl-benzene-1 ,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonic acid, 2-isopropyl- 5-methylphenol, 1 ,2,3,4-tetrahydro-naphthalene-1 ,5-diol, 2-chloro-benzene-1 ,3-diol, 4- hydroxy-naphthalene-1-sulfonic acid, benzene-1 ,2, 3-triol, naphthalene-2,3-diol, 5- dichloro-2-methyibenzene-1,3-diol, 4,6-dichlorobenzene-1 ,3-diol, and 2,3-dihydroxy- [1 ,4]naphthoquinone;
m-phenylenediamines such as: 2,4-diaminophenol, benzene-1 ,3- diamine, 2-(2,4-diamino-phenoxy)-ethanol, 2-[(3-amino-phenyl)-(2-hydroxy-ethyl)- amino]-ethanol, 2-mehyl-benzene-1 ,3-diamine, 2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2- hydroxy-ethyl)-amino]-ethanol, 4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1 ,3- diamine, 2-(2,4-diamino-phenyl)-ethanol, 2-(3-amino-4-methoxy-phenylamino)- ethanol, 4-(2-amino-ethoxy)-benzene-1 ,3-diamine, (2,4-diamino-phenoxy)-acetic acid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, 4-ethoxy-6-methyl-benzene- 1 ,3-diamine, 2-(2,4-diamino-5-methyl-phenoxy)-ethanol, 4,6-dimethoxy-benzene-1 ,3- diamine, 2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol, 3-(2,4-diamino- phenoxy)-propan-1 -ol, N-[3-(dimethylamino)phenyl]urea, 4-methoxy-6- methylbenzene-1 ,3-diamine, 4-fluoro-6-methylbenzene-1 ,3-diamine, 2-({3-[(2- hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol, 3-(2,4-diaminophenoxy)- propane-1 ,2-diol, 2-[2-amino-4-(methylamino)-phenoxy]ethanol, 2-[(5-amino-2- ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 2-[(3-aminophenyl)amino]ethanol, N- (2-aminoethyl)benzene-1 ,3-diamine, 4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene- 1 ,3-diamine, and 2,4-dimethoxybenzene-1 ,3-diamine;
m-aminophenols such as: 3-amino-phenol, 2-(3-hydroxy-4-methyl- phenylamino)-acetamide, 2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl- phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol, 3- amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 5-amino-2-(2-hydroxy- ethoxy)-phenol, 2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol, 5-amino-4-chloro-2- methyl-phenol, 3-cyclopentylamino-phenol, 5-[(2-hydroxyethyl)amino]-4-methoxy-2- methylphenol, 5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol, 3- (diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-ethoxy-2- methylphenol, 3-amino-2,4-dichloro-phenol, 3-[(2-methoxyethyl)amino]phenol, 3-[(2- hydroxyethyl)amino]phenol, 5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol, 5-[(3- hydroxypropyl)amino]-2-methylphenol, 3-[(3-hydroxy-2-methylphenyl)-amino]propane- 1 ,2-diol, and 3-[(2-hydroxyethyl)amino]-2-methylphenol; and
heterocyclic derivatives such as: 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol, 4- methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 6-methoxyquinolin-8-amine, 4- methylpyridine-2,6-diol, 2,3-dihydro-1 ,4-benzodioxin-5-ol, 1 ,3-benzodioxol-5-ol, 2-(1 ,3- benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol, 5-chloropyridine-2,3- diol, 2,6-dimethoxypyridine-3,5-diamine, 1 ,3-benzodioxol-5-amine, 2-{[3,5-diamino-6- (2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol, 1 H-indol-4-ol, 5-amino-2,6- dimethoxypyridin-3-ol, 1 H-indole-5,6-diol, 1 H-indol-7-ol, 1 H-indol-5-ol, 1 H-indol-6-ol, 6-broιmo-1 ,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-2,6-diamine, 3-[(3,5- diaminopyridin-2-yl)oxy]propane-1 ,2-diol, 5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1 ,3- diol, 1 H-indole-2,3-dione, indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine, 6- methoxypyridine-2,3-diamine, and 3,4-dihydro-2H-1 ,4-benzoxazin-6-amine.
Preferred primary intermediates include:
p-phenylenediamine derivatives such as: 2-methyl-benzene-1 ,4-diamine, benzene-1 ,4-diamine, 1 -(2,5-diamino-phenyl)-ethanol, 2-(2,5-diamino-phenyl)-ethanol, N-(2-methoxyethyl)benzene-1 ,4-diamine, 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)- amino]-ethanol, and 1 -(2, 5-diaminophenyl)ethane-1 ,2-diol;
p-aminophenol derivatives such as 4-amino-phenol, 4-methylamino- phenol, 4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol, and 1-(5-amino- 2-hydroxy-phenyl)-ethane-1 ,2-diol;
o-aminophenol derivatives such as: 2-amino-phenol, 2-amino-5-methyl- phenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2- amino-4-methyl-phenol;
heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine, 1-methyl-
1 H-pyrazole-4,5-diamine, 2-(4,5-diamino-1 H-pyrazol-1-yl)ethanol, 1-(4-methylbenzyl)- 1 H-pyrazole-4,5-diamine, 1-(benzyl)-1 H-pyrazole-4,5-diamine and N2,N2-dimethyl- pyridine-2,5-diamine.
Preferred couplers include:
phenols, resorcinol and naphthol derivatives such as: naphthalene-1 ,7- diol, benzene-1 ,3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl-naphthalen- 1-ol, naphthalene-1 ,5-dioI, naphthalene-2,7-diol, benzene-1 ,4-diol, 2-methyl-benzene- 1 ,3-diol, and 2-isopropyl-5-methylphenol; m-phenylenediamines such as: benzene-1 ,3-diamine, 2-(2,4-diamino- phenoxy)-ethanol, 4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1 ,3-diamine , 2-(3- amino-4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)- phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol;
m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol, 5- (2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol; and
heterocyclic derivatives such as: 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol, 4- methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1 ,3-benzodioxol-5-ol, 1 ,3-benzodioxol- 5-amine, 1 H-indol-4-ol, 1 H-indole-5,6-diol, 1 H-indol-7-ol, 1 H-indol-5-ol, 1 H-indol-6-ol, 1 H-indole-2,3-dione, pyridine-2,6-diamine,and 2-aminopyridin-3-ol.
Most preferred primary intermediates include:
p-phenylenediamine derivatives such as: 2-methyl-benzene-1 ,4-diamine, benzene-1 ,4-diamine, 2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)- ethanol, and 2-[(4-amino-phenyI)-(2-hydroxy-ethyl)-amino]-ethanol; p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino- phenol, 4-amino-3-methyl-phenol, and 1-(5-amino-2-hydroxy-phenyl)-ethane-1 ,2-diol;
o-aminophenols such as: 2-amino-phenol, 2-amino-5-methyl-phenol, 2- amino-6-methyI-phenol, and N-(4-amino-3-hydroxy-phenyl)-acetamide; and
heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine, 2-(4,5- diamino-1H-pyrazol-1-yl)ethanol, 1-(4-methyIbenzyl)-1 H-pyrazole-4,5-diamine, and 1- (benzyl)-1 H-pyrazole-4,5-diamine. Most preferred couplers include:
phenols, resorcinol and naphthol derivatives such as: benzene-1 ,3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol, and 2-methyl- benzene-1 ,3-diol;
m-phenylenediamine such as: 2-(2,4-diamino-phenoxy)-ethanol, 2-(3- amino-4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)- phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol;
m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol, 5- (2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol; and
heterocyclic derivatives such as: 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol, 4- methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1 H-indol-6-ol, and 2-aminopyridin-3-ol.
Understandably, the coupler compounds and the primary intermediate compounds, as well as the other dye compounds, in so far as they are bases, can be used as free bases or in the form of their physiologically compatible salts with organic or inorganic acids, such as hydrochloric acid or sulfuric acid, or, in so far as they have aromatic OH groups, in the form of their salts with bases, such as alkali phenolates.
The total amount of the combination of dye precursors (e.g., primary intermediate and coupler compounds) in the hair coloring compositions or systems of this invention is generally from about 0.001 to about 10, preferably from about 0.02 to about 10, and most preferably from about 0.2 to about 6.0 weight percent based on the total weight of the hair coloring composition. The primary intermediate and coupler compounds are generally used in equivalent amounts. However, it is possible to use the primary intermediate compounds in either excess or deficiency, i.e., a molar ratio of primary intermediate to coupler generally ranging from about 5:1 to about 1 :5.
The hair coloring compositions of this invention will contain the couplers of this invention in an effective coloring amount, generally in an amount of from about 0.001 to about 6 weight percent by weight of the hair dye composition, preferably from about 0.01 to about 3.5 weight percent. Other couplers, when present, are typically present in an amount such that in aggregate the concentration of couplers in the composition is from about 0.01 to about 6 weight percent. The primary intermediate(s) is present in an effective dyeing concentration generally an amount of from about 0.001 to about 6.0 weight percent by weight of the hair dye composition, preferably from about 0.01 to about 3.5 weight percent. Any suitable carrier or vehicle, generally an aqueous or hydroalcoholic solution, can be employed, preferably an aqueous solution. The carrier or vehicle will generally comprise up to about 40 weight percent.
The hair coloring compositions of this invention may contain one or more cationic, anionic or amphoteric surface active agents, perfumes, antioxidants, sequestering agents, thickening agents, alkalizing or acidifying agents, and other dyeing agents.
The compositions of the present invention are used by admixing them with a suitable oxidant, which reacts with the hair dye precursors to develop the hair dye. Any suitable peroxide providing agent can be employed in the coloring compositions of this invention, particularly hydrogen peroxide (H2O2) or precursors therefor. Also suitable are urea peroxide, sodium perborate, sodium percarbonate, and melamine peroxide.
Moreover, cosmetic additive ingredients, which are commonly used in compositions for coloring hair, can be used in the hair coloring compositions according to the invention, for example antioxidants, such as ascorbic acid, thioglycolic acid or sodium sulfite, and perfume oils, complex formers, wetting agents, emulsifiers, thickeners and care materials.
The form of the hair coloring compositions according to the invention can be, for example, a solution, especially an aqueous or aqueous-alcoholic solution. However, the form that is particularly preferred is a cream, gel or an emulsion. Its composition is a mixture of the dye ingredients with the conventional cosmetic additive ingredients suitable for the particular preparation.
Conventional cosmetic additive ingredients in solutions, creams, emulsion or gels include, for example:
Solvents: In addition to water, solvents that can be used are lower alkanols (e.g.,ethanol, propanol, isopropanol); polyols (e.g., carbitols, propylene glycol, glycerin). Under suitable processing, higher alcohols, such as cetyl alcohol, are suitable organic solvents, provided they are first liquified by melting, typically at low temperature (50 to 80 °C), before incorporation of other, usually lipophilic, materials. See WO 98/27941 (section on diluents) incorporated by reference.
Anionic and Nonionic Surfactants: These materials are from the classes of anionic, cationic, amphoteric or nonionic surfactant compounds, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzensulfonat.es, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanol amides and ethoxylated fatty acid esters. They are included for various reasons, e.g., to assist in thickening, for forming emulsions, to help in wetting hair during application of the hair dye composition, etc. Suitable materials are alkyl sulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, acyl isethionates, alkyl ethoxy carboxylates, fatty acid mono- and diethanolamides. Reference is made to WO 98/52523 published November 26, 1998 and incorporated herein by reference.
Thickeners: Suitable thickeners include such as higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oil, fatty acids and anionic and nonionic polymeric thickeners based on polyacrylic and polyurethane polymers. Examples are hydroxyethyl cellulose, hydroxymethylcellulose and other cellulose derivatives, hydrophobically modified anionic polymers and nonionic polymers, particularly such polymers having both hydrophilic and hydrophobic moieties (i.e., amphiphilic polymers). Useful nonionic polymers include polyurethane derivatives such as PEG- 150/stearyl alcohol/SDMI copolymer and PEG-150/stearyl alcohol SDMI copolymer. Other useful amphiphilic polymers are disclosed in US Pat. No. 6010541 incorporated by reference. Examples of anionic polymers that can be used as thickeners are acrylates copolymer, acrylates/ceteth-20 methacrylates copolymer, acrylates/ceteth- 20 itaconate copolymer, and acrylates/beheneth-25 acrylates copolymer. Aculyn® polymers sold by Rohm & Haas, as well as hair care materials, such as cationic resins, lanolin derivatives, cholesterol, pantothenic acids and betaine.
Alkalizing agents: Suitable materials that are used to increase pH of the hair dye compositions include ammonia, aminomethylpropanol, methylethanolamine, triethanolamine and ethanolamine.
Conditioners: Suitable materials include silicones and silicone derivatives; hydrocarbon oils; monomeric quaternary compounds, and quaternized polymers. Monomeric quaternary compounds are typically cationic compounds, but may also include betaines and other amphoteric and zwitterionic materials. Suitable monomeric quaternary compounds include behentrialkonium chloride, behentrimonium chloride, benzalkonium bromide or chloride, benzyl triethyl ammonium chloride, bis-hydroxyethyl tallowmonium chloride, C12-18 dialkyldimonium chloride, cetalkonium chloride, ceteartrimonium bromide and chloride, cetrimonium bromide, chloride and methosulfate, cetylpyridonium chloride, cocamidoproypl ethyldimonium ethosulfate, cocamidopropyl ethosulfate, coco-ethyldimonium ethosulfate, cocotrimonium chloride and ethosulfate, dibehenyl dimonium chloride, dicetyldimonium chloride, dicocodimonium chloride, dilauryl dimonium chloride, disoydimonium chloride, ditallowdimonium chloride, hydrogenated tallow trimonium chloride, hydroxyethyl cetyl dimonium chloride, myristalkonium chloride, olealkonium chloride, soyethomonium ethosulfate, soytrimonium chloride, stearalkonium chloride, and many other compounds. See WO 98/27941 incorporated by reference. Quatemized polymers are typically cationic polymers, but may also include amphoteric and zwitterionic polymers. Useful polymers are exemplified by polyquatemium-4, polyquaternium-6, polyquaternium-7, polyquatemium-8, polyquatemium-9, polyquaternium-10, polyquaternium-22, polyquaternium-32, polyquaternium-39, polyquaternium-44 and polyquatemium-47. Silicones suitable to condition hair are dimethicone, amodimethicone, dimethicone copolyol and dimethiconol. See also WO 99/34770 published July 15,1999, incorporated by reference, for suitable silicones. Suitable hydrocarbon oils would include mineral oil.
Natural ingredients: For example, protein derivatives, aloe, camomile and henna extracts.
Other adjuvants include acidulents to lower pH, buffers, chelating agents antioxidants, sequestrants, etc. These classes of materials and other species of materials in the classes referred to above but not specifically identified that are suitable are listed in the International Cosmetics Ingredient Dictionary and Handbook, (Eighth Edition) published by The Cosmetics, Toiletry, and Fragrance Association, incorporated by reference. In particular reference is made to Volume 2, Section 3 (Chemical Classes) and Section 4 (Functions) are useful in identifying a specific adjuvant/excipient to achieve a particular purpose or multipurpose.
The above-mentioned conventional cosmetic ingredients are used in amounts suitable for their purposes. For example the wetting agents and emulsifiers are used in concentrations of from about 0.5 to 30 percent by weight, the thickeners are used in an amount of from about 0.1 to 25 percent by weight and the hair care materials are used in concentrations of from about 0.1 to 5.0 percent by weight.
The hair coloring compositions according to the invention can be weakly acidic, neutral or alkaline according to their composition. The compositions typically have pH values of from 6.8 to 11.5. Their pH can be adjusted in the basic range with ammonia. Also, organic amines can be used for this purpose, including monoethanolamine and triethanolamine, or also inorganic bases, such as sodium hydroxide and potassium hydroxide. Inorganic or organic acids can be used for adjusting the pH in the acid range, for example phosphoric acid, acetic acid, citric acid or tartaric acid.
The hair coloring compositions of this invention will contain the couplers of this invention, alone or in combination with other couplers, in an effective coloring amount, generally in an amount of from about 0.01 to about 2.5 weight percent. Other couplers, when present will be present in an amount up to about 2.5 weight percent. The primary intermediate(s) will generally be present in an amount of from about 0.01 to about 3.5 weight percent. The molar ratio of primary intermediate to coupler will generally range from about 5:1 to about 1 :5 and be employed in any suitable carrier or vehicle, generally an aqueous or hydroalcoholic solution, preferably an aqueous solution. The carrier or vehicle will generally comprise up to about 40 weight percent.
In order to use the oxidation hair coloring composition for dyeing hair one mixes the above-described hair coloring compositions according to the invention with an oxidizing agent immediately prior to use and applies a sufficient amount of the mixture to the hair, according to the hair abundance, generally from about 60 to 200 grams. Some of the adjuvants listed above (e.g., thickeners, conditoners, etc.) can be provided in the dye composition or the developer, or both, depending on the nature of the ingredients, possible interactions, etc., as is well known in the art. Typically hydrogen peroxide, or its addition compounds with urea, melamine, sodium borate or sodium carbonate, can be used in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution as the oxidizing agent for developing the hair dye. Oxygen can also be used as the oxidizing agent. If a 6 percent hydrogen peroxide solution is used as oxidizing agent, the weight ratio of hair coloring composition and oxidizing agent is 5:1 to 1:2, but preferably 1 :1. The mixture of the oxidizing agent and the dye composition of the invention is allowed to act on the hair for about 10 to about 45 minutes, preferably about 30 minutes, at about 15 to 50°C, the hair is rinsed with water and dried. If necessary, it is washed with a shampoo and eventually after-rinsed with a weak organic acid, such as citric acid or tartaric acid. Subsequently the hair is dried.
The hair coloring composition according to the invention with a compound of formula (1) of this invention as coupler substances permits hair dyeing with outstanding color fastness, especially light fastness, fastness to washing and fastness to rubbing.
In general, a first composition of primary intermediate(s) and coupler(s) is prepared and then, at the time of use, the oxidizing agents, such as H2O2, is admixed therewith until an essentially homogenous composition is obtained which is applied to the hair to be dyed and permitted to remain in contact with the hair for a dyeing effective amount of time, generally for a period of from about 2 to 45, preferably about 2 to 30, minutes, after which the hair is rinsed, shampooed and dried. Optionally, a separate conditioning product may also be provided. Together the hair dye composition of the present invention comprising the hair dye coupler (1 ) and the developer comprising the oxidizing agent form a system for dyeing hair. This system may be provided as a kit comprising in a single package separate containers of the hair dye compositions, the developer, the optional conditioner or the hair treatment product, and instructions for use. Example 11
The following compositions shown in Table 1 can be used for dyeing Piedmont hair. The dyeing solution is mixed with 100 g 20 volume hydrogen peroxide. The resulting mixture is applied to the hair and permitted to remain in contact with the hair for 30 minutes. This dyed hair is then shampooed and rinsed with water and dried
TABLE 1 Composition for Dyeing Hair
Figure imgf000020_0001
Figure imgf000021_0001
1 In the aggregate, these ingredients are in the range of 2 to 15% by weight.
2 At least one of these dye precursors is typically present.
Exemplary combinations of hair coloring components employing a coupler compound of formula (1) of this invention are show in combinations in Table 1 and in C1 to C126 in Table A. Reading down the columns in Table A, the Xes designate the dye compounds (including the novel couplers of the instant invention) that form illustratively suitable combinations of dyes that can be formulated according to the present invention. For example, in Combination No. C1 the novel couplers of the present invention (Row 1 of Table A) with X, R, R1, R2 and R3 are as defined hereinbefore, can be combined with p-toluene diamine and 2-amino-phenol. Especially preferred as the couplers of formula (1) of this invention in the combinations C1 to C126 of Table A are:
1 -[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol~1 -ium chloride;
1-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride;
1-[2-(3-hydroxy-4-hydroxyethyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium chloride;
1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium bromide; 1-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl] -3 methyl 3-H-imidazol-1-ium iodide;
N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyI-N'-methyl-piperidinium chloride;
N-[2-(3-hydroxy-4-ethyl-phenylamino)-ethyl-N'-methyl-piperidinium chloride;
N-[2-(3-hydroxy-4-hydroxyethyl-phenylamino)-ethyl-N'-methyl-piperidinium chloride;
N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-piperidinium bromide; and N-[2-(3-hydroxy-4-methyl-phenylamino)-ethyl-N'-methyl-piperidinium iodide. Table A. DYE COMBINATIONS
Figure imgf000022_0001
Table A. DYE COMBINATIONS
Figure imgf000023_0001
Table A. DYE COMBINATIONS
Figure imgf000024_0001
Table A. DYE COMBINATIONS
Figure imgf000025_0001
Table A. DYE COMBINATIONS
Figure imgf000026_0001
Table A. DYE COMBINATIONS
Figure imgf000027_0001
Table A. DYE COMBINATIONS
Figure imgf000028_0001

Claims

We Claim:
A compound of formula (1 ):
Figure imgf000029_0001
d) wherein X is selected from the group consisting of halogen: R3 is selected from the group consisting of Ci to C2 alkyl and hydroxyethyl; and R, R1 and R2 are each independently selected from the group consisting of Ci to C22 alkyl or Ci to
C22 mono or dialkyl groups, or two of R, R1 and R2 together with the the nitrogen atom to which they are attached form a C3 to Cβ cycloaliphatic or a C3 to C14 aromatic group, the cycloaliphatic or aromatic group optionally containing in their rings one or more hetero atoms selected from O, S and N atoms
2. A compound of Claim 1 wherein X is selected from the group consisting of CI, Br, and I; and two of R, R1 and R2 together with the nitrogen atom to which they are attached form an C3 to Cβ cycloaliphatic or C3 to Cβ aromatic group optionally containing in the ring another N atom.
3. A compound of Claim 2 wherein X is CI.
4. A compound of Claim 3 wherein R3 is methyl.
5. A compound of Claim 4 wherein two of R, R1 and R2 together with the nitrogen atom to which they are attached form an imidazoline ring.
6. A compound of Claim 4 wherein two of R, R1 and R2 together with the nitrogen atom to which they are attached form a piperazine ring.
7. A process for the preparation of a compound of Claim 1 comprising reacting an aminophenol of the formula (2):
Figure imgf000030_0001
G)
with a haloacetyl chloride to produce a compound of formula (5)
Figure imgf000030_0002
(5)
reducing compound (5) with a borane-tetrahydrofuran complex to produce a compound of formula (6)
Figure imgf000031_0001
and reacting the compound of formula (6) with a reagent of the formula N(R1)(R2)(R3)to produce a compound of formula (1 )
Figure imgf000031_0002
d)
wherein X, R, R )1',
Figure imgf000031_0003
and R° are as defined in Claim 1 ,
8. A process according to Claim 7 wherein X is selected from the group consisting of CI, Br, and I; and two of R, R1 and R2 together with the nitrogen atom to which they are attached form an C3 to C6 cycloaliphatic or C3 to C6 aromatic group optionally containing in the ring another N atom.
9. A process according to Claim 8 wherein X is CI; R3 is methyl; and the other of R, R1 and R2 not forming the cycloaliphatic or aromatic group is methyl.
10. A process according to Claim 7 wherein the reducing agent is selected from the group consisting of sodium borohydride and sodium triacetoxyborohydride.
11. In a hair coloring system comprising a composition containing one or more oxidative hair coloring agents and a composition containing one or more oxidizing agents, the improvement comprising the presence in the composition containing one or more oxidative hair coloring agents of a coupler comprising a compound of formula (1):
Figure imgf000032_0001
d)
wherein X is selected from the group consisting of halogen; R3 is selected from the group consisting of Ci to C2 alkyl and hydroxyethyl; and R, R1 and R2 are each independently selected from the group consisting of Ci to C22 alkyl or Ci to C22 mono or dialkyl groups, or two of R, R1 and R2 together form a C3 to Cβ cycloaliphatic or a C3 to C14 aromatic group, the cycloaliphatic or aromatic group optionally containing in their rings one or more hetero atoms selected from O, S and N atoms. optionally containing in their rings one or more hetero atoms selected from O, S and N atoms.
12. A hair coloring system according to Claim 11 wherein the composition comprising one or more oxidative hair coloring agents additionally comprises one or more primary intermediates selected from the group consisting of: 2-methyl- benzene-1 ,4-diamine, benzene-1 , 4-diamine, 2-(2,5-diamino-phenyl)-ethanol, 1- (2,5-diamino-phenyl)-ethanol, 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]- ethanol, 4-amino-phenol, 4-methylamino-phenol, 4-amino-3-methyl-phenol, 1-(5- amino-2-hydroxy-phenyl)-ethane-1 ,2-diol, 2-amino-phenol, 2-amino-5-methyl- phenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine, 2-(4,5-diamino-1 H-pyrazol-1-yl)ethanol, 1-(4- methylbenzyl)-1 H-pyrazole-4,5-diamine, and 1-(benzyl)-1 H-pyrazole-4,5-diamine.
13. A hair coloring system according to Claim 12 wherein X is selected from the group consisting of CI, Br, and l; and two of R, R1 and R2 together with the nitrogen atom to which they are attached form an C3 to C cycloaliphatic or C3 to C aromatic group optionally containing in the ring another N atom.
14. In a system for coloring hair wherein at least one primary intermediate is reacted with at least one coupler in the presence of an oxidizing agent to produce an oxidative hair dye, the improvement wherein the at least one coupler comprises a compound of the formula (1 ):
Figure imgf000034_0001
d) wherein X is selected from the group consisting of halogen; R3 is selected from the group consisting of Ci to C2 alkyl and hydroxyethyl; and R, R1 and R2 are each independently selected from the group consisting of Ci to C22 alkyl or Ci to C22 mono or dialkyl groups ,or two of R, R and R2 together form a C3 to C6 cycloaliphatic or a C3 to Cι4 aromatic group, the cycloaliphatic or aromatic group optionally containing in their rings one or more hetero atoms selected from O, S and N atoms.
15. A system for coloring hair according to Claim 14 wherein the system additionally comprises one or more primary intermediates selected from the group consisting of: 2-methyl-benzene-1 ,4-diamine, benzene-1 ,4-diamine, 2- (2,5-diamino-phenyl)-ethanol, 1 -(2,5-diamino-phenyl)-ethanol, 2-[(4-amino- phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol, 4-methylamino- phenol, 4-amino-3-methyl-phenol, 1-(5-amino-2-hydroxy-phenyl)-ethane-1 ,2-diol, 2-amino-phenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol, N-(4- amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine, 2-(4,5- diamino-1 H-pyrazol-1 -yl)ethanol, 1 -(4-methylbenzyl)-1 H-pyrazole-4,5-diamine, and 1 -(benzyl)-1 H-pyrazole-4,5-diamine.
16. A system for coloring hair according to Claim 14 wherein the system contains one or more couplers selected from the group consisting of: benzene-1 , 3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl- naphthalen-1-ol, 2-methyl-benzene-1 ,3-diol, 2-(2,4-diamino-phenoxy)-ethanol, 2-(3-amino-4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy- ethoxy)-phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol, 3-amino- phenol, 5-amino-2-methyl-phenol, 5-(2-hydroxy-ethyIamino)-2-methyl-phenol, 3- amino-2-methyl-phenol, 3,4-dihydro-2H-1 ,4-benzoxazin-6-ol, 4-methyl-2-phenyl- 2,4-dihydro-3H-pyrazol-3-one, 1 H-indol-6-ol, and 2-aminopyridin-3-ol.
17. A system for coloring hair according to Claim 15 wherein the system contains one or more couplers selected from the group consisting of: benzene-1 ,3-diol, 4-chlorobenzene-1 ,3-diol, naphthalen-1-ol, 2-methyl- naphthalen-1-ol, 2-methyl-benzene-1 ,3-diol, 2-(2,4-diamino-phenoxy)-ethanol, 2-(3-amino-4-methoxy-phenyIamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy- ethoxy)-phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol, 3-amino- phenol, 5-amino-2-methyl-phenol, 5-(2-hydroxy-ethyIamino)-2-methyl-phenol, 3- amino-2-methyl-phenol, 3,4-dihydro-2H-1 ,4-benzoxazin-6-oI, 4-methyl-2-phenyl- 2,4-dihydro-3H-pyrazol-3-one, 1 H-indoI-6-ol, and 2-aminopyridin-3-ol.
18. A system for coloring hair according to Claim 15 wherein X is selected from the group consisting of CI, Br, and I; and two of R, R1 and R2 together with the nitrogen atom to which they are attached form an C3 to C6 cycloaliphatic or C3 to C6 aromatic group optionally containing in the ring another N atom.
19. A hair coloring composition for dyeing human hair comprising, in a suitable carrier or vehicle, a dyeing effective amount of:
(a) at least one primary intermediate,
(b) at least one coupler comprising a compound of the formula (1 ):
Figure imgf000036_0001
(1)
wherein X is selected from the group consisting of halogen; R3 is selected from the group consisting of Ci to C2 alkyl and hydroxyethyl; and R, R1 and R2 are each independently selected from the group consisting of Ci to C22 alkyl or C-i to C22 mono or dialkyl groups ,or two of R, R1 and R2 together form a C3 to Cβ cycloaliphatic or a C3 to C14 aromatic group, the cycloaliphatic or aromatic group optionally containing in their rings one or more hetero atoms selected from O, S and N atoms; and
(c) at least one oxidizing agent.
20. A hair coloring composition of Claim 19 wherein X is selected from the group consisting of CI, Br, and I; and two of R, R1 and R2 together with the nitrogen atom to which they are attached form an C3 to C6 cycloaliphatic or C3 to Cβ aromatic group optionally containing in the ring another N atom.
21. A process for dyeing human hair comprising applying a dyeing effective amount of a hair coloring composition of Claim 19 to the hair and permitting the composition to contact the hair for a dyeing effective period of time, and then rinsing, shampooing and drying the hair.
22. A process according to Claim 21 wherein X is selected from the group consisting of CI, Br, and I; and two of R, R1 and R2 together with the nitrogen atom to which they are attached form an C3 to Cβ cycloaliphatic or C3 to Q aromatic group optionally containing in the ring another N atom.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004019897A1 (en) * 2002-09-02 2004-03-11 Ciba Specialty Chemicals Holding Inc. Method of colouring porous material
FR2855406A1 (en) * 2003-06-02 2004-12-03 Oreal Oxidation dye composition useful for dyeing keratinic fibers, e.g. human hair, comprises one or more developers and a (new) imidazole coupler
US7238212B2 (en) 2003-06-02 2007-07-03 L'oreal, S.A. Imidazole compounds and use of these compounds for dyeing keratinous fibers
WO2013037907A1 (en) * 2011-09-15 2013-03-21 L'oreal Dye composition comprising a cationic para-aminophenol oxidation base

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021211393A1 (en) * 2020-04-12 2021-10-21 Pwai, Llc Hair color modification additive and related methods

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999048856A1 (en) * 1998-03-20 1999-09-30 L'oreal Oxidation dyeing compositions containing a cationic coupling agent, novel cationic coupling agents

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2315255A1 (en) 1975-06-26 1977-01-21 Oreal GLYCOLIC COUPLERS
FR2707490B1 (en) 1993-07-13 1995-09-22 Oreal Keratin fiber oxidation dye composition comprising a para-aminophenol, a meta-aminophenol and a 2-substituted para-aminophenol.
FR2715296B1 (en) 1994-01-24 1996-04-12 Oreal Keratin fiber oxidation dyeing composition comprising a paraphenylenediamine, a metalphenylenediamine and a para-aminophenol or a meta-aminophenol, and dyeing process using such a composition.
FR2788769B1 (en) * 1999-01-21 2001-02-16 Oreal NOVEL CATIONIC COUPLERS, THEIR USE FOR OXIDATION DYEING, DYEING COMPOSITIONS COMPRISING THE SAME, AND DYEING METHODS

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999048856A1 (en) * 1998-03-20 1999-09-30 L'oreal Oxidation dyeing compositions containing a cationic coupling agent, novel cationic coupling agents

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004019897A1 (en) * 2002-09-02 2004-03-11 Ciba Specialty Chemicals Holding Inc. Method of colouring porous material
US7229479B2 (en) 2002-09-02 2007-06-12 Ciba Specialty Chemicals Corporation Method of coloring porous material
FR2855406A1 (en) * 2003-06-02 2004-12-03 Oreal Oxidation dye composition useful for dyeing keratinic fibers, e.g. human hair, comprises one or more developers and a (new) imidazole coupler
EP1484049A1 (en) * 2003-06-02 2004-12-08 L'oreal Imidazole compounds and their use for dyeing of keratinous fibres
US7238212B2 (en) 2003-06-02 2007-07-03 L'oreal, S.A. Imidazole compounds and use of these compounds for dyeing keratinous fibers
WO2013037907A1 (en) * 2011-09-15 2013-03-21 L'oreal Dye composition comprising a cationic para-aminophenol oxidation base
FR2980199A1 (en) * 2011-09-15 2013-03-22 Oreal TINCTORIAL COMPOSITION COMPRISING A CATIONIC PARA-AMINOPHENOL OXIDATION BASE
US9271910B2 (en) 2011-09-15 2016-03-01 L'oreal Dye composition comprising a cationic para-aminophenol oxidation base

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