[go: up one dir, main page]

WO2005014591A1 - 2-acylamino or 2-sulfonylamino-1, 3-thiazoles as couplers for the oxidation dyeing of keratin fibres - Google Patents

2-acylamino or 2-sulfonylamino-1, 3-thiazoles as couplers for the oxidation dyeing of keratin fibres Download PDF

Info

Publication number
WO2005014591A1
WO2005014591A1 PCT/EP2004/007994 EP2004007994W WO2005014591A1 WO 2005014591 A1 WO2005014591 A1 WO 2005014591A1 EP 2004007994 W EP2004007994 W EP 2004007994W WO 2005014591 A1 WO2005014591 A1 WO 2005014591A1
Authority
WO
WIPO (PCT)
Prior art keywords
radical
amino
chloro
alkyl
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2004/007994
Other languages
French (fr)
Inventor
Jacqueline Mavro
Laurent Vidal
Jean-Baptiste Saunier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR0308606A external-priority patent/FR2857664B1/en
Application filed by LOreal SA filed Critical LOreal SA
Publication of WO2005014591A1 publication Critical patent/WO2005014591A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P5/00—Drugs for disorders of the endocrine system
    • A61P5/10—Drugs for disorders of the endocrine system of the posterior pituitary hormones, e.g. oxytocin, ADH
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/44—Acylated amino or imino radicals
    • C07D277/46—Acylated amino or imino radicals by carboxylic acids, or sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • C07D277/52—Nitrogen atoms bound to hetero atoms to sulfur atoms, e.g. sulfonamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/58—Nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to novel thiazole derivatives that are useful as couplers for the 5 oxidation dyeing of keratin fibres .
  • oxidation dye precursors in particular ortho- or para-phenylenediamines, ortho- or para- 10 a inophenols, heterocyclic compounds such as diaminopyrazole derivatives, pyrazolo [1, 5-a]pyrimidine derivatives , pyrimidine derivatives, pyridine derivatives, 5 , 6-dihydroxyindole derivatives and 5,6- dihydroxyindoline derivatives, which are generally 15 known as oxidation bases.
  • Oxidation dye precursors, or oxidation bases are colourless or weakly coloured compounds that, when combined with oxidizing products, can give rise to coloured compounds or dyes by a process of oxidative condensation. 20 It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers, the latter being chosen especially from meta-phenylenediamines, meta-aminophenols, meta-hydroxyphenols and certain 25 heterocyclic compounds such as, for example, pyrazolo- [1, 5-b] -1,2, 4-triazole derivatives, pyrazolo [3 , 2-c] - 1, 2, 4-triazole derivatives, pyrazolo [1, 5-a]pyrimidine derivatives, pyridine derivatives, pyrazol-5-one derivatives, indoline derivatives and indole derivatives .
  • couplers or coloration modifiers the latter being chosen especially from meta-phenylenediamines, meta-aminophenols, meta-
  • the variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.
  • the "permanent" coloration obtained with these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must have no toxicological drawbacks, it must allow shades to be obtained in the desired intensity,_ and it must show good resistance to external agents such as light, bad weather, washing, permanent-waving, perspiration and rubbing.
  • the dyes must also allow white hairs to be covered and, finally, they must be as unselective as possible, i.e. they must produce the smallest possible colour differences along the same length of keratin fibre, which may in fact be differently sensitized (i.e. damaged) between its end and its root.
  • the aim of the present invention is to provide novel couplers for obtaining an even wider range of shades and also dye compositions that produce powerful, uniform dyeing results between the root and the end of the hairs, which have good chromaticity, are sparingly selective and are particularly fast, while at the same time being capable of generating strong colorations in varied shades, in particular in the fundamental shades .
  • This aim is achieved with the present invention, one subject of which is a thiazole derivative of formula (I) below, and the addition salts thereof with an acid or a base :
  • Ri and R 2 which may be identical or different, represent : - a hydrogen atom; - a phenyl radical optionally substituted with one or more radicals chosen from halogens, hydroxyl, C 1 -C4 alkoxy, carboxyl, mono- or di (C 1 -C 4 ) alkyl- carboxamido (AlkHCO- or (Alk) 2 NCO), C 1 -C 4 thio- ether, (C1-C4) alkylsulphonyl (-S0 2 alkyl) , sulphonic (-S0 3 H) , alkyl sulphoxide (-SO-alkyl) , alkyl- sulphonamido ( (C 1 -C 4 ) alkylS0 2 NH-) and NR ⁇ 3 R ⁇ radicals, or a C 1 -C 4 alkyl radical optionally substituted with one or more hydroxyl, C 1 -C 4 alkoxy, carboxyl,
  • Ci-C ⁇ alkyl radical optionally substituted with one or more hydroxyl, C 1 -C 2 alkoxy, carboxyl, mono- or di (C 1 -C4) alkyl- carboxamido, (C1-C 4 ) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NR ⁇ 3 R ⁇ 4 radicals,
  • Ri and R 2 may form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle, one or more carbon atoms of the carbon-based ring of which may be replaced with an oxygen, nitrogen or sulphur atom or with an S0 2 group, the carbon atoms of the ring possibly being substituted with a radical R 4 and the ring not comprising a peroxide bond or diazo or nitroso radicals;
  • R 4 represents : - a halogen atom; - a C 1 -C 4 alkyl radical optionally substituted with one or more hydroxyl, carboxyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxy or NR5R6 radicals; - a carboxyl radical; - a mono- or di (C 1 -C 4 ) alkylcarboxamido radical; - a (C ⁇ -C 4 )alkylsulphonyl radical; - an alkylsulphonamido radical; - a hydroxyl radical; - a C1-C4 alkoxy radical; - a C2-C 4 hydroxyalkoxy radical; - an aminosulphonyl radical; - a C 1 -C4 thioether radical; - a (C 1 -C 4 ) alkyl sulphoxide radical; - a (C 1 -C 4 ) alkylsulph
  • R 3 represents a radical R 9 S0 2 H- or a radical Ri 0 C(O)NH- with R 9 and Rio, which may be identical or different, representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle, these radicals optionally being substituted with one or more radicals chosen from halogens, hydroxyl, C 1 -C 4 alkoxy, carboxyl, C 1 -C 4 alkoxycarbonyl, mono- or di (C 1 -C 4 ) alkylcarboxamido, (C ⁇ -C 4 )alkylsulphonyl, sulphonic, (C 1 -C 4 ) alkyl sulphoxide, C 1 -C 4 thioether, alkylsulphonamido or NR 11 R 12 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C 1 -C 4 alkoxy, carboxyl, mono- or di (C 1 -C
  • R 5 - R 5 , Re , R, Re, ii R12, Ri3 Ri4/ Ri6 and R i7 which may be identical or different, represent a hydrogen atom, a
  • R 7 and R 8 may also form, with the nitrogen atom that bears them, a 5- to 8-membered ring optionally substituted with one or more radicals chosen from halogens and hydroxyl, C ⁇ -C 2 alkoxy, carboxyl, alkyl- sulphonamido and NR 1 3R 14 radicals, or a C 1 -C 4 alkyl radical optionally substituted with one or more hydroxyl, C 1 -C 4 alkoxy, carboxyl, mono- or di(C ⁇ -C 4 )- alkylcarboxamido or NR 1 3R 14 ;
  • X represents a hydrogen atom; a halogen atom (such as fluorine, chlorine or bromine) ; a C 1 -C 4 alkoxy radical; a phenoxy radical optionally substituted with one or more radicals chosen from halogens and hydroxyl, C 1 -C 4 alkoxy, carboxyl, C1-C 4 alkoxycarbonyl, mono-
  • a subject of the present invention is also a dye composition comprising, in a medium that is suitable for dyeing,
  • thiazole derivative of formula (I) as defined above.
  • a subject of the invention is also dyeing processes using this composition.
  • Another subject of the invention is the use of the derivatives of formula (I) for the oxidation dyeing of keratin fibres, in particular human keratin fibres such as the hair.
  • the thiazole derivatives of formula (I) of the invention suitable for use as couplers for the oxidation dyeing of keratin fibres, but also they produce particularly strong and sparingly selective colorations. Furthermore, they make it possible to obtain dye compositions which produce colorations that show good fastness with respect to the various attacking factors to which the hair may be subjected, such as light, bad weather, washing or perspiration.
  • the oxidation dye compositions in accordance with the invention furthermore make it possible to obtain shades in a very wide range of colours.
  • the alkyl radical may be linear or branched and optionally substituted with a hydroxyl, alkoxy or carboxyl.
  • these radicals may be identical or different.
  • radicals Ri and R 2 of formula (I) examples include hydrogen and a methyl, ethyl, (iso)propyl, 2-hydroxyethyl, 1-hydroxy- ethyl, 2-carboxyethyl, 2-aminoethyl, 2- (dimethy1- amino) ethyl, 2- (acylamino) ethyl , 2-methoxyethy1, 1, 2-dihydroxyethyl, l-hydroxy-2-aminoethyl, 2-hydroxy- 1-aminoethyl, acetyl or phenyl radical.
  • Ri and R 2 of formula (I) examples include hydrogen and a methyl, ethyl, (iso)propyl, 2-hydroxyethyl, 1-hydroxy- ethyl, 2-carboxyethyl, 2-aminoethyl, 2- (dimethy1- amino) ethyl, 2- (acylamino) ethyl , 2-me
  • R 2 which may be identical or different, represent: - a hydrogen atom; - a phenyl radical optionally substituted with one or more radicals chosen from halogens and hydroxyl, C 1 -C4 alkoxy, carboxyl, (C1-C 4 ) alkylcarboxamido, (C 1 -C 4 ) alkylsulphonyl, sulphonic, alkyl sulphoxide, C 1 -C 4 thioether, alkylsulphonamido and NR ⁇ 3 Ri4 radicals, or a C 1 -C 4 alkyl radical optionally substituted with one or more hydroxyl, C3.-C 4 alkoxy, carboxyl, mono- or di(C ⁇ -C 4 )- alkylcarboxamido, (C 1 -C 4 ) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NR ⁇ 3 Ri 4 ,-
  • R 2 which may be identical or different, represent a hydrogen atom; a phenyl radical; a linear or branched C 3. -C 4 alkyl radical, optionally substituted with one or more hydroxyl, C 1 -C 2 alkoxy, amino, di (C 1 -C 4 ) alkylamino, carboxyl, (C3.-C 4 ) alkylcarboxamido, (C 1 -C 4 ) alkylsulphonamido or N 13 R 14 radicals in which R i3 and R ⁇ 4 , which may be identical or different, represent a hydrogen atom, (C1-C 4 ) alkyl-CO or a C3.-C2 alkyl radical optionally substituted with a hydroxyl or a C1-C2 alkoxy.
  • Ri and R 2 which may be identical or different, represent a hydrogen atom or an optionally substituted alkyl radical, for example methyl, 2-hydroxyethyl, 2-carboxyethyl or 1,2-di- hydroxyethyl , or phenyl.
  • Ri and R 2 form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle chosen from pyrrolidine, piperidine, homopiperidine, piperazine and homopiperazine, the said rings possibly being substituted with one or more radicals R .
  • Ri and R 2 form, together with the nitrogen, atom to which they are attached, a heterocycle chosen from pyrrolidine, 2 , 5-dimethylpyrrolidine, proline, 3- hydroxyproline, 4-hydroxyproline, 2,4- dicarboxypyrrolidine, 3-hydroxy-2- hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine, 2- (diethyl- carboxamido)pyrrolidine, 2-hydroxymethylpyrrolidine, 3 , 4-dihydroxy-2-hydroxymethylpyrrolidine, 3-hydroxy- pyrrolidine, 3 , 4-dihydroxypyrrolidine, 3-amino- pyrrolidine, 3-methylaminopyrrolidine, 4-amino-3- hydroxypyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) - a inopyrrolidine, piperidine, 2 , 6-dimethylpiperidine, 2-carb ⁇ xypiperidine, 2-carboxamidopiperidine, 2-hydroxymethyl
  • Ri and R 2 form, together with the nitrogen atom to which they are attached, a heterocycle chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-amino- pyrrolidine, proline, 3-hydroxyproline, piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, homopiperidine, homopiperazine,, N-methylhomopiperazine and N- ⁇ -hydroxyethylhomopiperazine, and the addition salts thereof .
  • a heterocycle chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-amino- pyrrolidine, proline, 3-hydroxyproline, piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, homopiperidine, homopiperazine,, N-methylhomopiperazine and N- ⁇ -hydroxyethylhomopiperazine, and the addition salts thereof .
  • R 3 examples that may be mentioned for R 3 include the radicals R 9 S0 2 NH- or a radical R ⁇ 0 C(O)NH- with R 9 and Rio, which may be identical or different, chosen from a methyl, methyl, ethyl, (iso)propyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-carboxyethyl, 2-aminoethyl, 2- (dimethylamino ) ethyl , 2- (acylamino) ethyl , 2-methoxyethy1 , phenyl, 4-aminophenyl, 4-hydroxyphenyl, 4-diethyl- aminophenyl, pyrazolyl, thiazolyl, pyridyl or thienyl.
  • R 9 S0 2 NH- or a radical R ⁇ 0 C(O)NH- with R 9 and Rio which may be identical or different, chosen from a methyl, methyl, ethyl, (
  • R 3 is an aromatic heterocycle, it is preferably chosen from pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl and thienyl heterocycles .
  • R 3 represents a radical R 9 S0 2 NH- or a radical R ⁇ 0 C(O)NH-; with Rg and Rio, which may be identical or different, ' representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle such as pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, i idazolyl or thienyl, these radicals being optionally substituted with one or more radicals chosen from halogens and hydroxyl, C1-C 4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido or R 11 R 12 radicals, or a C 1 -C4 alkyl radical
  • Ci-C ⁇ alkyl radical substituted with one or more radicals chosen from hydroxyl, C ⁇ -C 2 alkoxy, carboxyl, mono- or di (C 1 -C 4 ) alkylcarboxamido, (C 1 -C 4 ) alkylsulphonyl, sulphonic, (C 1 -C 4 ) alkyl sulphoxide, alkyl- sulphonamide and NR ⁇ 6 R ⁇ radicals;
  • R11, Ri2/ R-13/ Ri4# R-16 and R i7 which may be identical or different, represent a hydrogen atom, acyl, a carboxamido or a C 1 -C 4 alkyl radical optionally substituted with one or more hydroxyl, C 1 -C 4 alkoxy, (C 1 -C 4 ) alkylsulphonyl, (C 1 -C 4 ) alkylsulphonamido, carboxyl, mono- or di (C 1 -C 4 ) alkylcarboxamido, (C 1 -C 4 ) alkyl sulphoxide, amino, (di) (C 1 -C 4 ) alkylamino or (poly)hydroxy (C 2 -C 4 ) alkylamino radicals .
  • R 3 represents a radical RgS0 2 NH- or a radical R ⁇ oC(0)NH- with Rg and R 10 , which may be identical or different, chosen from an alkyl radical, a phenyl radical, a pyrazolyl radical, a thiazolyl radical, a pyridyl radical or a thienyl radical, these radicals possibly being substituted.
  • R 10 represents a methyl, ethyl, 2-hydroxyethyl, 2-carboxyethyl, phenyl, pyrazolyl, thienyl or pyridyl radical and Rg represents a methyl, phenyl or tolyl radical.
  • X preferably represents a hydrogen atom, a chlorine atom or an alkoxy radical, for example methoxy.
  • X preferably represents a hydrogen atom, a chlorine atom or an alkoxy radical, for example methoxy.
  • the thiazole derivative corresponds to formula (lb)
  • a derivative of formula (I) of the invention that is more particularly preferred is 5- (pyrrolidin- 1-yl) -2- (thien-2-yl) acylaminothiazole and the addition salts thereof .
  • Another subject of the invention is a dye composition comprising, in a suitable medium, at least one oxidation base and, as coupler, at least one thiazole derivative of formula (I) .
  • the composition of the present invention is particularly useful for the oxidation dyeing of keratin fibres and in particular of human keratin fibres .
  • the oxidation bases that may be used in the composition of the present invention are the oxidation bases conventionally used in oxidation dyeing.
  • these oxidation bases are chosen from oxidation bases, for example para-phenylenediamines, bis (phenyl) alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof with an acid or a base.
  • para-phenylenediamines that may be mentioned, are pa a-phenylenediamine, para-tolylene- diamine, 2-chloro-para-phenylenediamine, 2, 3-dimethyl- para-phenylenediamine, 2 , 6-dimethyl-para-phenylene- diamine, 2 , 6-diethyl-para-phenylenediamine, 2,5-di- methyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, N,N-diethyl-3- methyl-para-phenylenediamine, N,N-bis ( ⁇ -hydroxyethyl) - para-phenylenediamine, N,N-bis ( ⁇ -hydroxyethyl) -2- methyl-para-phenylenediamine, N,N-
  • para-phenylenediamine para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2- ⁇ -hydroxyethyl- para-phenylenediamine, 2- ⁇ -hydroxyethyloxy-para- phenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2 , 6-diethyl-para-phenylenediamine, 2 , 3-dimethyl-para- phenylenediamine, N,N-bis ( ⁇ -hydroxyethyl) -para- phenylenediamine, 2-chloro-para-phenylenediamine and 2- ⁇ -acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid or a base, are particularly preferred.
  • the bis (phenyl) alkylenediamines that may be mentioned, for example, are N,N' -bis ( ⁇ -hydroxyethyl) -N,N' -bis (4'-aminophenyl) -1, 3-diaminopropanol, N,N' -bis ( ⁇ -hydroxyethyl) -N,N' -bis (4 ' -aminophenyl) - ethylenediamine, N,N' -bis (4-aminophenyl) tetramethylenediamme, N,N' -bis ( ⁇ -hydroxyethyl) -N,N' -bis (4-amino- phenyl) tetramethylenediamine, N,N' -bis (4-methylamino- phenyl) tetramethylenediamine, N,N' -bis (ethyl) -N,N' -bis- (4 ' -amino-3 ' - -
  • ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5- ethylphenol, 2-amino-6-methylphenol and 5-acetamido-2- a inophenol, and the addition salts thereof with an acid or a base.
  • heterocyclic bases for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives .
  • pyridine ' derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-di- aminopyridine, 2- (4-methoxyphenyl) amino-3-amino- pyridine, 2, 3-diamino-6-methoxypyridine, 2- ( ⁇ -methoxy- ethyl) amino-3-amino-6-methoxypyridine and 3,4-diamino- pyridine, and the addition salts thereof with an acid or a base.
  • pyrimidine derivatives that can be mentioned are the compounds described, for example, in patents DE 2 359 399; JP 88-169 571; JP 05-163 124; EP 0 770 375 or patent application WO 96/15765, such as 2,4,5, 6-tetraaminopyrimidine, 4-hydroxy-2 , 5 , 6-triamino- pyrimidine, 2-hydroxy-4, 5 , 6-triaminopyrimidine, 2,4-di- hydroxy-5 , 6-diaminopyrimidine and 2,5, 6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo [1, 5-a] - pyrimidi ⁇ ie-3 , 7-diamine; 2 , 5-dimethylpyrazolo [1, 5-a] - pyrimidine-3, 7-diamine; pyrazolo [1, 5-a]pyrimidine
  • pyrazole derivatives that may be mentioned are the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4, 5-diamino-l-methylpyrazole, 4, 5-diamino-l- ( ⁇ -hydroxyethyl) pyrazole, 3,4-diamino- pyrazole, 4, 5-diamino-l- (4 ' -chlorobenzyl)pyrazole, 4, 5-diamino-l, 3-dimethylpyrazole, 4, 5-diamino-3-methyl- 1-phenylpyrazole, 4, 5-diamino-l-methyl-3-phenyl- pyrazole, 4-amino-1, 3-dimethyl-5-hydrazinopyrazole, l-benzyl-4, 5-diamino-3-methylpyrazole, 4, 5-dia
  • the oxidation base(s) is (are) each generally present in an amount of between 0.001% and 10% and preferably between 0.005% and 6% by weight approximately relative to the total weight of the dye composition.
  • the composition according to the invention may also contain one or more couplers conventionally used for oxidation dyeing of human keratin fibres .
  • couplers conventionally used for oxidation dyeing of human keratin fibres .
  • additional couplers mention may be made especially of meta-phenylenediamines, meta-amino- phenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers other than the thiazole derivatives of formula (I) of the invention, and the addition salts thereof with an acid or a base.
  • Examples that may be mentioned include 2-methyl-5-aminophenol, 5-N- ( ⁇ -hydroxyethyl) amino- 2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1, 3-dihydroxybenzene, 1, 3-dihydroxy- 2-methylbenzene, 4-chloro-l, 3-dihydroxybenzene, 2 , 4-diamino-l- ( ⁇ -hydroxyethyloxy)benzene, 2-amino- 4- ( ⁇ -hydroxyethylamino) -1-methoxybenzene, 1, 3-diamino- benzene, 1, 3-bis (2, 4-diaminophenoxy)propane, 3-ureido- aniline, 3-ureido-l-dimethylaminobenzene, sesamol, l- ⁇ -hydroxyethylamino-3 , 4-methylenedioxybenzene, ⁇ -naphthol, 2-methyl-l-naphthol, 6-hydroxyind
  • the coupler (s) is (are) each generally present in an amount ranging from 0.001% to 10% by weight approximately, and more preferably from 0.005% to 6% by weight, relative to the total weight of the dye composition.
  • the addition salts of the oxidation bases and couplers that may be used in the context of the invention are chosen especially from the addition salts with an acid, such as the hydro- chlorides, hydrobromides , sulphates, citrates, succinates, tartrates, lactates, tosylates, benzene- sulphonates, phosphates and acetates, and the addition salts with a base, such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines .
  • the dye composition according to the invention may also contain one or more direct dyes, which may be chosen in particular from nitrobenzene dyes, azo direct dyes and methine direct dyes. These direct dyes may be of nonionic, anionic or cationic nature.
  • the medium that is cosmetically suitable for dyeing also known as the dye support, generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds that would not be sufficiently soluble in water.
  • organic solvent mention may be made, for example, of C1-C4 lower alkanols, such as ethanol and isopropanol, polyol ⁇ and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents are preferably present in proportions of between 1% and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5% and 30% by weight approximately.
  • the dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidant ⁇ , penetration agents, sequestering agents, fragrances, buffers, dispersing agents, conditioners, for instance volatile or non- volatile, modified or unmodified silicones, film- forming agents, ceramides, preserving agents and opacifiers .
  • adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic, cationic, nonionic, amphoteric or
  • the above adjuvants are generally present in an amount for each of between 0.01% and 20% by weight relative to the weight of the composition. Needless to say, a person skilled in the art will take care to select this or these optional additional compound (s) such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition (s) .
  • the pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately and preferably between 5 and 11 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratin fibres, or alternatively using standard buffer systems.
  • acidifying agents are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids.
  • the dye composition according to the invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair.
  • the process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibres, in the presence of an oxidizing agent for a time which is sufficient to obtain the desired coloration.
  • the colour may be revealed at acidic, neutral or alkaline pH and the oxidizing agent may be added to the composition of the invention just at the time of use, or it may be introduced using an oxidizing composition containing it, applied simultaneously with or sequentially to the composition of the invention.
  • the composition according to the present invention is mixed, preferably at the time of use, with acomposition containing, in a medium that is suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount that is sufficient to develop a coloration.
  • the mixture obtained is then applied to the keratin fibres.
  • the oxidizing agents conventionally used for the oxidation dyeing of keratin fibres are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, peracids, and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases. Hydrogen peroxide is particularly preferred.
  • the oxidizing composition may also contain various adjuvants conventionally used in hair dye compositions and as defined above.
  • the pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibres preferably ranges between 3 and 12 approximately and even more preferably between 5 and 11. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres and as defined above.
  • the ready-to-use composition that is finally applied to the keratin fibres may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair.
  • a subject of the invention is also a multi- compartment device or dyeing "kit", in which a first compartment contains the dye composition defined above and a second compartment contains an oxidizing agent.
  • This device may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR 2 586 913 in the name of the Applicant .
  • Using this device it is possible to dye keratin fibres using a process that involves mixing a dye composition comprising at least one oxidation base of formula (I) with an oxidizing agent, and applying the mixture obtained to the keratin fibres for a time that is sufficient to develop the desired coloration.
  • the derivatives of formula (I) may be obtained according to the synthetic methods known in the field of heterocyclic synthesis.
  • a first method consists in treating 2,4-di- chlorothiazole with nitric acid to give 5-nitro-2, 4-di- chlorothiazole 2, which reacts at temperatures of between 0°C and 130°C in a polar solvent, with primary, secondary or tertiary amines, and in particular with ammonia, to give the 2-amino-4-chloro-5-nitrothiazole compounds 3_.
  • the acylation reaction of the a ine in position 2 is performed according to the standard methods (for example, refer to Advanced Organic 1
  • the compounds of formula 7 are obtained by reaction of alkyl or arylsulphonyl halides with the amine 3>, in aprotic solvents with a boiling point of between 45°C and 180°C. The reactions for reduction of the nitrothiazole group 7 and then for alkylation of the amine thus obtained are performed as mentioned above. 2 3 1
  • the compounds 10 are obtained by heterogeneous catalytic hydrogenation of the compounds 4 (or 7, respectively) , the catalyst possibly being, for example, palladium-on-charcoal, Raney nickel or palladium dihydroxide, in a polar solvent with a boiling point of between 60°C and 180°C,
  • the 5-aminothiazole derivatives 10 and 12 are then reacted with electrophiles (halides, O-sulphonates, etc.) to give the desired compounds 11 and 13.
  • a second method consists in reacting commercial 2-amino-5-bromothiazole 14 with nitric acid in the presence of tetrafluoroboric acid and copper to give the nitro derivative 15.
  • the bromine becomes labile and is reacted with amines NHR ⁇ R 2 in polar solvents with boiling points of between 65°C and 180°C, to give the 2-nitro-5-aminothiazole derivatives ,16.
  • the reduction of the nitro group via standard methods (Reduction in Organic Chemistry, M. Hudlicky, Ellis Horwood series chemical Science) , for example via heterogeneous catalytic hydrogenation with Pd(0) or Pd(II) on charcoal, gives the diamine compounds 17.
  • the acylation reaction of the amine in position 2 is performed according to the standard methods (for example, refer to Advanced Organic Chemistry, 3rd edi tion, J. March, Willey Interscience) with an acyl chloride R ⁇ 0 -COCl or an anhydride (R ⁇ 0 -CO) 2 -O, in aprotic solvents with a boiling point of between 45°C and 180°C, to give the compounds of formula 18.
  • the compounds of formula 21 are obtained via reaction of alkyl or arylsulphonyl halides with the amine 17 in aprotic solvents with a boiling point of between 45°C and 180°C.
  • the introduction of the halogen atom into position 4 of the thiazole derivatives 18 and 21 is performed via the action of N-chlorosuccinimide or N-bromosuccinimide according to the standard methods, and allows access to compounds 19 and 22.
  • the introduction of an alkoxy, aryloxy or alkylthio group is performed via substitution of the halogen with the corresponding alkoxide or thioalkoxide anion and allows compounds 2TJ and 2Z_ to be obtained.
  • Example 2 The compositions below were prepared using the above compound:

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Engineering & Computer Science (AREA)
  • Diabetes (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Medicinal Chemistry (AREA)
  • Endocrinology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention relates to thiazole derivatives of formula (I) that are useful as couplers for the oxidation dyeing of keratin fibres.The invention also relates to a dye composition containing at least one oxidation base and at least one thiazole derivative as coupler, to the use of this composition for dyeing keratin fibres and to the dyeing process using this composition.

Description

2-ACYLAMINO OR 2-SULFONYLAMINO-l , 3-THIAZOLES AS COUPLERS FOR THE OXIDATION DYEING OF KERATIN FIBRES
The invention relates to novel thiazole derivatives that are useful as couplers for the 5 oxidation dyeing of keratin fibres . It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular ortho- or para-phenylenediamines, ortho- or para- 10 a inophenols, heterocyclic compounds such as diaminopyrazole derivatives, pyrazolo [1, 5-a]pyrimidine derivatives , pyrimidine derivatives, pyridine derivatives, 5 , 6-dihydroxyindole derivatives and 5,6- dihydroxyindoline derivatives, which are generally 15 known as oxidation bases. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds that, when combined with oxidizing products, can give rise to coloured compounds or dyes by a process of oxidative condensation. 20 It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers, the latter being chosen especially from meta-phenylenediamines, meta-aminophenols, meta-hydroxyphenols and certain 25 heterocyclic compounds such as, for example, pyrazolo- [1, 5-b] -1,2, 4-triazole derivatives, pyrazolo [3 , 2-c] - 1, 2, 4-triazole derivatives, pyrazolo [1, 5-a]pyrimidine derivatives, pyridine derivatives, pyrazol-5-one derivatives, indoline derivatives and indole derivatives . The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained. The "permanent" coloration obtained with these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must have no toxicological drawbacks, it must allow shades to be obtained in the desired intensity,_ and it must show good resistance to external agents such as light, bad weather, washing, permanent-waving, perspiration and rubbing. The dyes must also allow white hairs to be covered and, finally, they must be as unselective as possible, i.e. they must produce the smallest possible colour differences along the same length of keratin fibre, which may in fact be differently sensitized (i.e. damaged) between its end and its root. They must also show good chemical stability in the formulations, and must have a good toxicological profile. The aim of the present invention is to provide novel couplers for obtaining an even wider range of shades and also dye compositions that produce powerful, uniform dyeing results between the root and the end of the hairs, which have good chromaticity, are sparingly selective and are particularly fast, while at the same time being capable of generating strong colorations in varied shades, in particular in the fundamental shades . This aim is achieved with the present invention, one subject of which is a thiazole derivative of formula (I) below, and the addition salts thereof with an acid or a base :
Figure imgf000004_0001
(l)
in which:
• Ri and R2, which may be identical or different, represent : - a hydrogen atom; - a phenyl radical optionally substituted with one or more radicals chosen from halogens, hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkyl- carboxamido (AlkHCO- or (Alk)2NCO), C1-C4 thio- ether, (C1-C4) alkylsulphonyl (-S02alkyl) , sulphonic (-S03H) , alkyl sulphoxide (-SO-alkyl) , alkyl- sulphonamido ( (C1-C4) alkylS02NH-) and NRι3Rι radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (Cι-C4)alkyl- carboxamido, '(C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NRι3Ri4;
- a linear or branched Ci-Cβ alkyl radical optionally substituted with one or more hydroxyl, C1-C2 alkoxy, carboxyl, mono- or di (C1-C4) alkyl- carboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NRι3Rι4 radicals,
- Ri and R2 may form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle, one or more carbon atoms of the carbon-based ring of which may be replaced with an oxygen, nitrogen or sulphur atom or with an S02 group, the carbon atoms of the ring possibly being substituted with a radical R4 and the ring not comprising a peroxide bond or diazo or nitroso radicals;
- R4 represents : - a halogen atom; - a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, carboxyl, C1-C4 alkoxycarbonyl, C1-C4 alkoxy or NR5R6 radicals; - a carboxyl radical; - a mono- or di (C1-C4) alkylcarboxamido radical; - a (Cι-C4)alkylsulphonyl radical; - an alkylsulphonamido radical; - a hydroxyl radical; - a C1-C4 alkoxy radical; - a C2-C4 hydroxyalkoxy radical; - an aminosulphonyl radical; - a C1-C4 thioether radical; - a (C1-C4) alkyl sulphoxide radical; - a (C1-C4) alkylsulphonyl radical; - a radical NR7R8;
• R3 represents a radical R9S02 H- or a radical Ri0C(O)NH- with R9 and Rio, which may be identical or different, representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle, these radicals optionally being substituted with one or more radicals chosen from halogens, hydroxyl, C1-C4 alkoxy, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (Cι-C4)alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, C1-C4 thioether, alkylsulphonamido or NR11R12 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NR13R14, - a linear or branched Ci-Cs alkyl radical optionally substituted with one or more hydroxyl, OR15, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, alkyl- sulphona ido or NRι6 i7 radicals; with R15 representing a C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, Cι-C2 alkoxy, amino, (di) (C1-C4) alkylamino and (poly)hydroxy (C2-C4) - alkylamino radicals;
- R5, Re , R, Re, ii R12, Ri3 Ri4/ Ri6 and Ri7, which may be identical or different, represent a hydrogen atom, a
(Cι-C )alkylsulphonyl or (C1-C4) alkyl-CO radical, a mono- or di (C1-C4) alkylcarboxamido radical, or a C3.-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, (C1-C4) alkylsulphonyl, (C1-C4)- alkylsulphonamido, carboxyl, mono- or (di) (C1-C4) alkylcarboxamido, (C1-C4) alkyl sulphoxide, amino, (di)(Cχ-C4)- alkylamino or (poly)hydroxy (C2-C ) alkylamino;
- R7 and R8 may also form, with the nitrogen atom that bears them, a 5- to 8-membered ring optionally substituted with one or more radicals chosen from halogens and hydroxyl, Cι-C2 alkoxy, carboxyl, alkyl- sulphonamido and NR13R14 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di(Cι-C4)- alkylcarboxamido or NR13R14; X represents a hydrogen atom; a halogen atom (such as fluorine, chlorine or bromine) ; a C1-C4 alkoxy radical; a phenoxy radical optionally substituted with one or more radicals chosen from halogens and hydroxyl, C1-C4 alkoxy, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, C1-C4 thioether, alkyl- sulphonamido, NR13R1 and C1-C4 alkyl radicals; a C1-C4 thioether radical optionally substituted with a hydroxyl, Cχ-C2 alkoxy, carboxyl, sulphonic or amino radical, with the exception of the derivatives
Figure imgf000008_0001
A subject of the present invention is also a dye composition comprising, in a medium that is suitable for dyeing,
- at least one oxidation base, and
- as coupler, at least one thiazole derivative of formula (I) as defined above. A subject of the invention is also dyeing processes using this composition. Another subject of the invention is the use of the derivatives of formula (I) for the oxidation dyeing of keratin fibres, in particular human keratin fibres such as the hair. Not only are the thiazole derivatives of formula (I) of the invention suitable for use as couplers for the oxidation dyeing of keratin fibres, but also they produce particularly strong and sparingly selective colorations. Furthermore, they make it possible to obtain dye compositions which produce colorations that show good fastness with respect to the various attacking factors to which the hair may be subjected, such as light, bad weather, washing or perspiration. The oxidation dye compositions in accordance with the invention furthermore make it possible to obtain shades in a very wide range of colours. In the radicals defined above bearing an alkyl group, and unless otherwise indicated, the alkyl radical may be linear or branched and optionally substituted with a hydroxyl, alkoxy or carboxyl. Furthermore, when the molecule contains several radicals of the same name, for example NRι3Ri4, these radicals may be identical or different. Examples that may be mentioned for the radicals Ri and R2 of formula (I) include hydrogen and a methyl, ethyl, (iso)propyl, 2-hydroxyethyl, 1-hydroxy- ethyl, 2-carboxyethyl, 2-aminoethyl, 2- (dimethy1- amino) ethyl, 2- (acylamino) ethyl , 2-methoxyethy1, 1, 2-dihydroxyethyl, l-hydroxy-2-aminoethyl, 2-hydroxy- 1-aminoethyl, acetyl or phenyl radical. According to one particular embodiment, Ri and
R2, which may be identical or different, represent: - a hydrogen atom; - a phenyl radical optionally substituted with one or more radicals chosen from halogens and hydroxyl, C1-C4 alkoxy, carboxyl, (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, C1-C4 thioether, alkylsulphonamido and NRχ3Ri4 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C3.-C4 alkoxy, carboxyl, mono- or di(Cι-C4)- alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NRι3Ri4,- - a linear or branched Ci-Cβ alkyl radical optionally substituted with one or more hydroxyl, Cι-C2 alkoxy, carboxyl, (C1-C4) alkylcarboxamido, (C3.-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or Rχ3Ri4 radicals. According to one preferred embodiment, i and
R2, which may be identical or different, represent a hydrogen atom; a phenyl radical; a linear or branched C3.-C4 alkyl radical, optionally substituted with one or more hydroxyl, C1-C2 alkoxy, amino, di (C1-C4) alkylamino, carboxyl, (C3.-C4) alkylcarboxamido, (C1-C4) alkylsulphonamido or N 13R14 radicals in which Ri3 and Rχ4, which may be identical or different, represent a hydrogen atom, (C1-C4) alkyl-CO or a C3.-C2 alkyl radical optionally substituted with a hydroxyl or a C1-C2 alkoxy. Preferably, Ri and R2, which may be identical or different, represent a hydrogen atom or an optionally substituted alkyl radical, for example methyl, 2-hydroxyethyl, 2-carboxyethyl or 1,2-di- hydroxyethyl , or phenyl. According to another embodiment, Ri and R2 form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle chosen from pyrrolidine, piperidine, homopiperidine, piperazine and homopiperazine, the said rings possibly being substituted with one or more radicals R . As examples of this particular embodiment, Ri and R2 form, together with the nitrogen, atom to which they are attached, a heterocycle chosen from pyrrolidine, 2 , 5-dimethylpyrrolidine, proline, 3- hydroxyproline, 4-hydroxyproline, 2,4- dicarboxypyrrolidine, 3-hydroxy-2- hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine, 2- (diethyl- carboxamido)pyrrolidine, 2-hydroxymethylpyrrolidine, 3 , 4-dihydroxy-2-hydroxymethylpyrrolidine, 3-hydroxy- pyrrolidine, 3 , 4-dihydroxypyrrolidine, 3-amino- pyrrolidine, 3-methylaminopyrrolidine, 4-amino-3- hydroxypyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) - a inopyrrolidine, piperidine, 2 , 6-dimethylpiperidine, 2-carbόxypiperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethyl- piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxy- homopiperidine, 2-carboxamidohomopiperidine, homo- piperazine, N-methylhomopiperazine and N-β-hydroxyethylhomopiperazine, and the addition salts thereof. Preferably, Ri and R2 form, together with the nitrogen atom to which they are attached, a heterocycle chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-amino- pyrrolidine, proline, 3-hydroxyproline, piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, homopiperidine, homopiperazine,, N-methylhomopiperazine and N-β-hydroxyethylhomopiperazine, and the addition salts thereof . Examples that may be mentioned for R3 include the radicals R9S02NH- or a radical Rι0C(O)NH- with R9 and Rio, which may be identical or different, chosen from a methyl, methyl, ethyl, (iso)propyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-carboxyethyl, 2-aminoethyl, 2- (dimethylamino ) ethyl , 2- (acylamino) ethyl , 2-methoxyethy1 , phenyl, 4-aminophenyl, 4-hydroxyphenyl, 4-diethyl- aminophenyl, pyrazolyl, thiazolyl, pyridyl or thienyl. According to one particular embodiment, when
R3 is an aromatic heterocycle, it is preferably chosen from pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl and thienyl heterocycles . According to one preferred embodiment, R3 represents a radical R9S02NH- or a radical Rι0C(O)NH-; with Rg and Rio, which may be identical or different, ' representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle such as pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, i idazolyl or thienyl, these radicals being optionally substituted with one or more radicals chosen from halogens and hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido or R11R12 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido or NRι3Ri4 radicals;
- a linear or branched Ci-Cβ alkyl radical substituted with one or more radicals chosen from hydroxyl, Cι-C2 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, alkyl- sulphonamide and NRι6Rι radicals;
- R11, Ri2/ R-13/ Ri4# R-16 and Ri7, which may be identical or different, represent a hydrogen atom, acyl, a carboxamido or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, (C1-C4) alkylsulphonyl, (C1-C4) alkylsulphonamido, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkyl sulphoxide, amino, (di) (C1-C4) alkylamino or (poly)hydroxy (C2-C4) alkylamino radicals . According to one particular embodiment, R3 represents a radical RgS02NH- or a radical RιoC(0)NH- with Rg and R10, which may be identical or different, chosen from an alkyl radical, a phenyl radical, a pyrazolyl radical, a thiazolyl radical, a pyridyl radical or a thienyl radical, these radicals possibly being substituted. Preferably, R10 represents a methyl, ethyl, 2-hydroxyethyl, 2-carboxyethyl, phenyl, pyrazolyl, thienyl or pyridyl radical and Rg represents a methyl, phenyl or tolyl radical. In formula (I) above, X preferably represents a hydrogen atom, a chlorine atom or an alkoxy radical, for example methoxy. Among the derivatives of formula (I) that are useful in the present invention, in particular in the composition of the invention, mention may be made of the following compounds:
5-amino-2-methylsulphonylaminothiazole
5-amino-2-phenylsulphonylaminothiazole
5-amino-2-tolylsulphonylaminothiazole 5-amino-2-thiazolylsulphonylaminothiazole 5-amino-2-pyridylsulphonylaminothiazole
5-amino-2-phenacylaminothiazole 5-amino-2- (pyrid-2-yl) acylaminothiazole 5-amino-2- (pyrid-3-yl) acylaminothiazole 5-amino-2- (pyrid-4-yl) acylaminothiazole 5-amino-2-acetylaminothiazole 5-amino-2-isopropylacylaminothiazole -amino-2- (thien-2-yl) acylaminothiazole -methylamino-2-methylsulphonylaminothiazole 5-methylamino-2-phenylsulphonylaminothiazole 5-methylamino-2-tolylsulphonylaminothiazole
5-methylamino-2-thiazolylsulphonylaminothiazole 5-methylamino-2-pyridylsulphonylaminothiazole 5-methylamino-2-phenacylaminothiazole 5-methylamino-2- (pyrid-2-yl) acylaminothiazole 5-methylamino-2- (pyrid-3-yl) acylaminothiazole 5-methylamino-2- (pyrid-4-yl) acylaminothiazole 5-methylamino-2-acetylaminothiazole 5-methylamino-2-isopropylacylaminothiazole 5-methylamino-2- (thien-2-yl) acylaminothiazole
5- (2-hydroxyethyl) amino-2-methylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-phenylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-tolylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-thiazolylsulphonylamino- thiazole
5- (2-hydroxyethyl) amino-2-pyridylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-phenacylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-3-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-4-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-2-isopropylacylaminothiazole - (2-hydroxyethyl) amino-2- (thien-2-yl) acylaminothiazole -amino-4-chloro-2-methylsulphonylaminothiazole -amino-4-chloro-2-phenylsulphonylaminothiazole -amino-4-chloro-2-tolylsulphonylaminothiazole -amino-4-chloro-2-thiazolylsulphonylaminothiazole -amino-4-chloro-2-pyridylsulphonylaminothiazole -amino-4-chloro-2-phenacylaminothiazole -amino-4-chloro-2- (pyrid-2-yl) acylaminothiazole -amino-4-chloro-2- (pyrid-3-yl) acylaminothiazole -amino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5-amino-4-chloro-2-acetylaminothiazole 5-amino-4-chloro-2-isopropylacylaminothiazole 5-amino-4-chloro-2- (thien-2-yl) acylaminothiazole
5-methylamino-4-chloro-2-methylsulphonylaminothiazole 5-methylamino-4-chloro-2-phenylsulphonylaminothiazole 5-methylamino-4-chloro-2-tolylsulphonylaminothiazole 5-methylamino-4-chloro-2-thiazolylsulphonylamino- thiazole 5-methylamino-4-chloro-2-pyridylsulphonylaminothiazole 5-methylamino-4-chloro-2-phenacylaminothiazole 5-methylamino-4-chloro-2- (pyrid-2-yl) acylaminothiazole 5-methylamino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5-methylamino-4-chloro-2- (pyrid-4-yl) cylaminothiazole 5-methylamino-4-chloro-2-acetylaminothiazole
5-methylamino-4-chloro-2-isopropylacylaminothiazole 5-methylamino-4-chloro-2- (thien-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-methylsulphonyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-phenylsulphonyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-tolylsulphonyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-thiazolylsulphonyl- aminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-pyridylsulphonyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-phenacylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-2-yl)acyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-3-yl) acylaminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-isopropylacyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2- (thien-2-yl) acylaminothiazole
5- (pyrrolidin-1-yl) -2-methylsulphonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenylsulphonylaminothiazole - (pyrrolidin-1-yl) -2-tolylsulphonylaminothiazole - (pyrrolidin-1-yl) -2-thiazolylsulphonylaminothiazole - (pyrrolidin-1-yl) -2-pyridylsulphonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenacylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-3-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-4-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2-acetylaminothiazole 5- (pyrrolidin-1-yl) -2-isopropylacylaminothiazole 5- (pyrrolidin-1-yl) -2- (thien-2-yl) acylaminothiazole
5- (pyrrolidin-1-yl) -4-chloro-2-methylsulphonylamino- thiazole
5- (pyrrolidin-1-yl) -4-chloro-2-phenylsulphonylamino- thiazole
5- (pyrrolidin-1-yl) -4-chloro-2-tolylsulphonylamino- thiazole
5- (pyrrolidin-1-yl) -4-chloro-2-thiazolylsulphonyl- aminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-pyridylsulphonylamino- thiazole
5- (pyrrolidin-1-yl) -4-chloro-2-phenacylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-3-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-4-yl) acylamino- thiazole
5- (pyrrolidin-1-yl) -4-chloro-2-acetylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-isopropylacylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (thien-2-yl) acylaminothiazole and also the addition salts thereof with an acid or a base. According to one particular embodiment, the thiazole derivative corresponds to formula (lb)
Figure imgf000019_0001
(lb)
in which R3 is as defined above. A derivative of formula (I) of the invention that is more particularly preferred is 5- (pyrrolidin- 1-yl) -2- (thien-2-yl) acylaminothiazole and the addition salts thereof . Another subject of the invention is a dye composition comprising, in a suitable medium, at least one oxidation base and, as coupler, at least one thiazole derivative of formula (I) . The composition of the present invention is particularly useful for the oxidation dyeing of keratin fibres and in particular of human keratin fibres . The oxidation bases that may be used in the composition of the present invention are the oxidation bases conventionally used in oxidation dyeing. By way of example, these oxidation bases are chosen from oxidation bases, for example para-phenylenediamines, bis (phenyl) alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof with an acid or a base. Among the para-phenylenediamines that may be mentioned, are pa a-phenylenediamine, para-tolylene- diamine, 2-chloro-para-phenylenediamine, 2, 3-dimethyl- para-phenylenediamine, 2 , 6-dimethyl-para-phenylene- diamine, 2 , 6-diethyl-para-phenylenediamine, 2,5-di- methyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, N,N-diethyl-3- methyl-para-phenylenediamine, N,N-bis (β-hydroxyethyl) - para-phenylenediamine, N,N-bis (β-hydroxyethyl) -2- methyl-para-phenylenediamine, N,N-bis (β-hydroxyethyl) - 2-chloro-para-phenylenediamine, 2-β-hydroxyethyl-para- phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) - para-phenylenediamine, 2-hydroxymethy1-para- phenylenediamine, N,N-dimethyl-3-methyl-para- phenylenediamine, N-ethyl-N- (β-hydroxyethyl) -para- phenylenediamine, N- (β,γ-dihydroxypropyl) -para- phenylenediamine, N- (4 ' -aminophenyl) -para- phenylenediamine, N-phenyl-para-phenylenediamine, 2-β- hydroxyethyloxy-para-phenylenediamine, 2-β-acetylamino- ethyloxy-para-phenylenediamine, N- (β-methoxyethyl)para- phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl- para-phenylenediamine, 2-β-hydroxyethylamino-5-amino- toluene, and the addition salts thereof with an acid or a base. Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl- para-phenylenediamine, 2-β-hydroxyethyloxy-para- phenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2 , 6-diethyl-para-phenylenediamine, 2 , 3-dimethyl-para- phenylenediamine, N,N-bis (β-hydroxyethyl) -para- phenylenediamine, 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid or a base, are particularly preferred. Among the bis (phenyl) alkylenediamines that may be mentioned, for example, are N,N' -bis (β-hydroxyethyl) -N,N' -bis (4'-aminophenyl) -1, 3-diaminopropanol, N,N' -bis (β-hydroxyethyl) -N,N' -bis (4 ' -aminophenyl) - ethylenediamine, N,N' -bis (4-aminophenyl) tetramethylenediamme, N,N' -bis (β-hydroxyethyl) -N,N' -bis (4-amino- phenyl) tetramethylenediamine, N,N' -bis (4-methylamino- phenyl) tetramethylenediamine, N,N' -bis (ethyl) -N,N' -bis- (4 ' -amino-3 ' - ethylphenyl) ethylenediamine and 1, 8-bis- (2 , 5-diaminophenoxy) -3 , 6-dioxaoctane, and the addition salts thereof with an acid or a base. Among the para-aminophenols that may be mentioned, for example, are para-aminophenol, 4-amino- 3-methylphenol, 4-amino-3-fluorophenol, 4-amino-
3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino- 2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4^amino-2- (β-hydroxyethyl- aminomethyl)phenol and 4-amino-2-fluorophenol, and the addition' salts thereof with an acid or a base. Among the ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5- ethylphenol, 2-amino-6-methylphenol and 5-acetamido-2- a inophenol, and the addition salts thereof with an acid or a base. Among the heterocyclic bases that may be mentioned, for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives . Among the pyridine ' derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-di- aminopyridine, 2- (4-methoxyphenyl) amino-3-amino- pyridine, 2, 3-diamino-6-methoxypyridine, 2- (β-methoxy- ethyl) amino-3-amino-6-methoxypyridine and 3,4-diamino- pyridine, and the addition salts thereof with an acid or a base. Among the pyrimidine derivatives that can be mentioned are the compounds described, for example, in patents DE 2 359 399; JP 88-169 571; JP 05-163 124; EP 0 770 375 or patent application WO 96/15765, such as 2,4,5, 6-tetraaminopyrimidine, 4-hydroxy-2 , 5 , 6-triamino- pyrimidine, 2-hydroxy-4, 5 , 6-triaminopyrimidine, 2,4-di- hydroxy-5 , 6-diaminopyrimidine and 2,5, 6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo [1, 5-a] - pyrimidiιie-3 , 7-diamine; 2 , 5-dimethylpyrazolo [1, 5-a] - pyrimidine-3, 7-diamine; pyrazolo [1, 5-a]pyrimidine-3 , 5- diamine; 2, 7-dimethylpyrazolo [1, 5-a]pyrimidine-3 , 5- diamine; 3-aminopyrazolo [1, 5-a]pyrimidin-7-ol; 3-amino- pyrazolo [1, 5-a]pyrimidin-5-ol; 2- (3-aminopyrazolo- [1, 5-a]pyrimidin-7-ylamino) ethanol, 2- (7-aminopyrazolo- [1, 5-a]pyrimidin-3-ylamino) ethanol, 2-[ (3-aminopyrazolo [1, 5-a]pyrimidin-7-yl) (2-hydroxyethyl) amino] - ethanol, 2- [ (7-aminopyrazolo [1, 5-a]pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5, 6-dimethylpyrazolo- [1, 5-a] pyrimidine-3 , 7-diamine, 2 , 6-dimethylpyrazolo- tl, 5-a]pyrimidine-3 , 7-diamine, 2, 5,N7,N7-tetramethyl- pyrazolo.l, 5-a]pyrimidine-3, 7-diamine and 3-amino- 5-methyl-7-imidazolylpropylaminopyrazolo [1, 5-a] - pyrimidine, and the addition salts thereof with an acid and the tautomeric forms thereof, when a tautomeric equilibrium exists. Among the pyrazole derivatives that may be mentioned are the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4, 5-diamino-l-methylpyrazole, 4, 5-diamino-l- (β-hydroxyethyl) pyrazole, 3,4-diamino- pyrazole, 4, 5-diamino-l- (4 ' -chlorobenzyl)pyrazole, 4, 5-diamino-l, 3-dimethylpyrazole, 4, 5-diamino-3-methyl- 1-phenylpyrazole, 4, 5-diamino-l-methyl-3-phenyl- pyrazole, 4-amino-1, 3-dimethyl-5-hydrazinopyrazole, l-benzyl-4, 5-diamino-3-methylpyrazole, 4, 5-diamino-3- tert-butyl-1-methylpyrazole, 4, 5-diamino-l-tert-butyl- 3-methylpyrazole, 4, 5-diamino-l- (β-hydroxyethyl) - 3-methylpyrazole, 4, 5-diamino-l-ethyl-3-methylpyrazole, 4, 5-diamino-l-ethyl-3- (4' -methoxyphenyl)pyrazole, 4, 5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4, 5-diamino-3-hydroxymethyl-l-methylpyrazole, 4, 5-diamino-3-hydroxymethyl-l-isopropylpyrazole, 4, 5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5- (2 ' -aminoethyl) amino-1, 3-dimethylpyrazole, 3 , 4, 5-triaminopyrazole, 1-methyl-3 , 4, 5-triamino- pyrazole, 3 , 5-diamino-l-methyl-4-methylaminopyrazole and 3 , 5-diamino-4- (β-hydroxyethyl) amino-1-methyl- pyrazole, and the addition salts thereof with an acid or a base. The oxidation base(s) is (are) each generally present in an amount of between 0.001% and 10% and preferably between 0.005% and 6% by weight approximately relative to the total weight of the dye composition. The composition according to the invention may also contain one or more couplers conventionally used for oxidation dyeing of human keratin fibres . Among these additional couplers, mention may be made especially of meta-phenylenediamines, meta-amino- phenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers other than the thiazole derivatives of formula (I) of the invention, and the addition salts thereof with an acid or a base. Examples that may be mentioned include 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino- 2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1, 3-dihydroxybenzene, 1, 3-dihydroxy- 2-methylbenzene, 4-chloro-l, 3-dihydroxybenzene, 2 , 4-diamino-l- (β-hydroxyethyloxy)benzene, 2-amino- 4- (β-hydroxyethylamino) -1-methoxybenzene, 1, 3-diamino- benzene, 1, 3-bis (2, 4-diaminophenoxy)propane, 3-ureido- aniline, 3-ureido-l-dimethylaminobenzene, sesamol, l-β-hydroxyethylamino-3 , 4-methylenedioxybenzene, α-naphthol, 2-methyl-l-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino- 3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-di- amino-2, 6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino- 3, 4-methylenedioxybenzene and 2, 6-bis (β-hydroxyethylamino) toluene and the addition salts thereof with an acid or a base. In the composition of the present invention, the coupler (s) is (are) each generally present in an amount ranging from 0.001% to 10% by weight approximately, and more preferably from 0.005% to 6% by weight, relative to the total weight of the dye composition. In general, the addition salts of the oxidation bases and couplers that may be used in the context of the invention are chosen especially from the addition salts with an acid, such as the hydro- chlorides, hydrobromides , sulphates, citrates, succinates, tartrates, lactates, tosylates, benzene- sulphonates, phosphates and acetates, and the addition salts with a base, such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines . The dye composition according to the invention may also contain one or more direct dyes, which may be chosen in particular from nitrobenzene dyes, azo direct dyes and methine direct dyes. These direct dyes may be of nonionic, anionic or cationic nature. The medium that is cosmetically suitable for dyeing, also known as the dye support, generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds that would not be sufficiently soluble in water. As organic solvent, mention may be made, for example, of C1-C4 lower alkanols, such as ethanol and isopropanol, polyolε and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The solvents are preferably present in proportions of between 1% and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5% and 30% by weight approximately. The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidantε, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, conditioners, for instance volatile or non- volatile, modified or unmodified silicones, film- forming agents, ceramides, preserving agents and opacifiers . The above adjuvants are generally present in an amount for each of between 0.01% and 20% by weight relative to the weight of the composition. Needless to say, a person skilled in the art will take care to select this or these optional additional compound (s) such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition (s) . The pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately and preferably between 5 and 11 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratin fibres, or alternatively using standard buffer systems. Among the acidifying agents that may be mentioned, for example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids. Among the basifying agents that may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the derivatives of formula (II) below:
Figure imgf000029_0001
R<= Rd(ll)
in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb Re and Ra, which may be identical or different, .represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical. The dye composition according to the invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair. The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibres, in the presence of an oxidizing agent for a time which is sufficient to obtain the desired coloration. The colour may be revealed at acidic, neutral or alkaline pH and the oxidizing agent may be added to the composition of the invention just at the time of use, or it may be introduced using an oxidizing composition containing it, applied simultaneously with or sequentially to the composition of the invention. According to one particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with acomposition containing, in a medium that is suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount that is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres. After a leave-in time of 3 to 50 minutes approximately and preferably 5 to 30 minutes approximately, the keratin fibres are rinsed, washed with shampoo, rinsed again and then dried. The oxidizing agents conventionally used for the oxidation dyeing of keratin fibres are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, peracids, and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases. Hydrogen peroxide is particularly preferred. The oxidizing composition may also contain various adjuvants conventionally used in hair dye compositions and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibres preferably ranges between 3 and 12 approximately and even more preferably between 5 and 11. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres and as defined above. The ready-to-use composition that is finally applied to the keratin fibres may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair. A subject of the invention is also a multi- compartment device or dyeing "kit", in which a first compartment contains the dye composition defined above and a second compartment contains an oxidizing agent. This device may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR 2 586 913 in the name of the Applicant . Using this device, it is possible to dye keratin fibres using a process that involves mixing a dye composition comprising at least one oxidation base of formula (I) with an oxidizing agent, and applying the mixture obtained to the keratin fibres for a time that is sufficient to develop the desired coloration. The derivatives of formula (I) may be obtained according to the synthetic methods known in the field of heterocyclic synthesis. Reference may be made, for example, to the publications EP 1256578, US 61143665, WO 97/47299, EP 402716, DE 3842970, DE 3518520, Khimico Farmaberticheskii Zhurnal 1983, 17(11), 1340-2, J. Org. Chem. , 1975, 40(9), 1275-8. The derivatives of the present invention are obtained, for example, from thiazole reagents substituted with a nitro radical, which are reduced via standard reduction methods . A first method consists in treating 2,4-di- chlorothiazole with nitric acid to give 5-nitro-2, 4-di- chlorothiazole 2, which reacts at temperatures of between 0°C and 130°C in a polar solvent, with primary, secondary or tertiary amines, and in particular with ammonia, to give the 2-amino-4-chloro-5-nitrothiazole compounds 3_. The acylation reaction of the a ine in position 2 is performed according to the standard methods (for example, refer to Advanced Organic 1
Chemistry, 3rd edition, J. March, Willey Interscience) with an acyl chloride Rι0-COCl or an anhydride (Rιo-C0)2-0, in aprotic solvents with a boiling point of between 45°C and 180°C, to give the compounds of formulae 4. The nitro group is then reduced via the action of a metal such as iron, tin or zinc and in the catalytic presence of an acid such as protic acids, for instance HC1, HBr or NH4CI, to give the 5-amino-4- chloro-2-acylaminothiazoles 5. This product is then subjected to a standard alkylation reaction (for example, refer to Advanced Organic Chemistry, 3rd edition, J. March, Willey Interscience) with alkyl halides or alkyl O-sulphonates to give the desired compounds 6. The compounds of formula 7 are obtained by reaction of alkyl or arylsulphonyl halides with the amine 3>, in aprotic solvents with a boiling point of between 45°C and 180°C. The reactions for reduction of the nitrothiazole group 7 and then for alkylation of the amine thus obtained are performed as mentioned above.
Figure imgf000033_0001
2 3 1
Figure imgf000033_0002
8 The compounds 10 (or 12, "respectively) are obtained by heterogeneous catalytic hydrogenation of the compounds 4 (or 7, respectively) , the catalyst possibly being, for example, palladium-on-charcoal, Raney nickel or palladium dihydroxide, in a polar solvent with a boiling point of between 60°C and 180°C, The 5-aminothiazole derivatives 10 and 12 are then reacted with electrophiles (halides, O-sulphonates, etc.) to give the desired compounds 11 and 13.
Figure imgf000034_0001
Figure imgf000034_0002
A second method consists in reacting commercial 2-amino-5-bromothiazole 14 with nitric acid in the presence of tetrafluoroboric acid and copper to give the nitro derivative 15. The bromine becomes labile and is reacted with amines NHRιR2 in polar solvents with boiling points of between 65°C and 180°C, to give the 2-nitro-5-aminothiazole derivatives ,16. The reduction of the nitro group via standard methods (Reduction in Organic Chemistry, M. Hudlicky, Ellis Horwood series chemical Science) , for example via heterogeneous catalytic hydrogenation with Pd(0) or Pd(II) on charcoal, gives the diamine compounds 17. The acylation reaction of the amine in position 2 is performed according to the standard methods (for example, refer to Advanced Organic Chemistry, 3rd edi tion, J. March, Willey Interscience) with an acyl chloride Rι0-COCl or an anhydride (Rι0-CO)2-O, in aprotic solvents with a boiling point of between 45°C and 180°C, to give the compounds of formula 18. The compounds of formula 21 are obtained via reaction of alkyl or arylsulphonyl halides with the amine 17 in aprotic solvents with a boiling point of between 45°C and 180°C. The introduction of the halogen atom into position 4 of the thiazole derivatives 18 and 21 is performed via the action of N-chlorosuccinimide or N-bromosuccinimide according to the standard methods, and allows access to compounds 19 and 22. The introduction of an alkoxy, aryloxy or alkylthio group is performed via substitution of the halogen with the corresponding alkoxide or thioalkoxide anion and allows compounds 2TJ and 2Z_ to be obtained. Λ f NM"> UUNNOO,, BΓ"^ ^fΛ\' if- 1 0υ== NN1111..00IH1 R "''R">'N"^^ S"V /f Nm0»> ""'' R WΛN~^-^rT"S -NH, PάlC
„
Figure imgf000035_0001
21 22 X, * Cl, Br .- X = OR, OΛr,SR Finally, a subject of the invention is the intermediate nitro derivatives of formula:
Figure imgf000036_0001
in which R9 and RIO are as defined above. The examples that follow serve to illustrate the invention without, however, being limiting in nature . EXAMPLES 1 mmol of 5-nitro-2- (thien-2-yl) acylaminothiazole derivative is added to 10 ml of an aqueous- alcoholic solution (80/20 ethanol/water) containing 10% of protic acid such as hydrochloric acid, ammonium chloride, acetic acid or sulphuric acid, and 0.5 g of zinc in powder form, at a temperature of 80°C. After total consumption of the nitro starting material, the reaction mixture is concentrated until a solid precipitates out, which is filtered off by suction, washed with diisopropyl ether and dried under vacuum to constant weight. 5-Amino-2- (thien-2-yl) acylaminothiazole (C8H7N3OS2) is thus obtained: 95% yield.
Figure imgf000036_0002
Examples of dyeing Example 1 The compositions below were prepared using the above compound:
Figure imgf000037_0001
( * ) Dye support (1) pH 9.5 DMSO 0.18 g 96° ethyl alcohol 9.3 g Methyl alcohol 39.7 g Acetic acid 4.4 g Sodium metabisulphite 0.204 g Pentasodium salt of diethylene 1.1 g triaminopentaacetic acid, as an aqueous 40% solution C.8-C15 alkyl polyglucoside sold as 5.3 g 60% solution under the name Oramix CG110 by the company SEPPIC Benzyl alcohol 1.8 g Polyethylene glycol containing 2.7 g 8 mol of EO pH 9.5 buffer of NH4Cl/aqueous 31.0 g ammonia containing 20% NH3 At the time of use, the composition is mixed with one third of its weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight) . The mixture obtained is applied to a lock of grey hair containing 90% white hairs. After a leave-in time of 30 minutes, the lock is rinsed, washed with a standard shampoo, rinsed again and then dried. The shade obtained is dark purple. Example 2 The compositions below were prepared using the above compound:
Figure imgf000038_0001
(*) Dye support (2) pH 7 DMSO 0.18 g 96° ethyl alcohol 9.3 g Methyl alcohol 39.7 g Acetic acid 4.4 g Sodium metabisulphite 0.204 g Pentasodium salt of diethylene 1.1 g triaminopentaacetic acid, as an aqueous 40% solution Cs-Ci5 alkyl polyglucoside sold as 5.3 g 60% solution under the name Oramix CGI10 by the company SEPPIC Benzyl alcohol 1.8 g Polyethylene glycol containing 2.7 g 8 mol of EO pH 7 buffer of 0.5M ammonium 31.0 g chloride At the time of use, the composition is mixed with one third of its weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight) . The mixture obtained is applied to a lock of grey hair containing 90% white hairs. After a leave-in time of 30 minutes, the lock is rinsed, washed with a standard shampoo, rinsed again and then dried. The shade obtained is dark purple.

Claims

CLAIMS 1. Thiazole derivative of formula (I) below, and the addition salts thereof with an acid or a base:
Figure imgf000040_0001
(l)
in which:
• Ri and R2, which may be identical or different, represent: - a hydrogen atom; - a phenyl radical optionally substituted with one or more radicals chosen from halogens, hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, C1-C4 thioether, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido and NR13R14 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NR13R14; - a linear or branched Ci-Cs alkyl radical optionally substituted with one or more hydroxyl, Cι-C2 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NR13R14 radicals,
- Ri and R2 may form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle, one or more carbon atoms of the carbon-based ring of which may be replaced with an oxygen, nitrogen or sulphur atom or with an S02 group, the carbon atoms of the ring possibly being substituted with a radical R4 and the ring not comprising a peroxide bond or diazo or nitroso radicals;
- R4 represents : - a halogen atom; - a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, carboxyl, C1-C4 alkoxycarbonyl, C1-C4 alkoxy or NR5R6 radicals; - a carboxyl radical; - a mono- or di (C1-C4) alkylcarboxamido radical; - a (C1-C4) alkylsulphonyl radical; - an alkylsulphonamido radical; - a hydroxyl radical; - a C1-C4 alkoxy radical; - a C2-C4 hydroxyalkoxy radical; - an aminosulphonyl radical; - a C1-C4 thioether radical; - a (C1-C4) alkyl sulphoxide radical; - a (C1-C4) alkylsulphonyl radical; - a radical NR7R8; • R3 represents a radical R9S02NH- or a radical RιoC(0)NH- with Rg and Rι0, which may be identical or different, representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle, these radicals optionally being substituted with one or more radicals chosen from halogens, hydroxyl, C1-C4 alkoxy, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, C1-C4 thioether, alkylsulphonamido or NR11R12 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkyl- carboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NRι3Ri , - a linear or branched Cι-C8 alkyl radical optionally substituted with one or more hydroxyl, OR15, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, alkylsulphonamido or NRi6Rι7 radicals; with R15 representing a C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, Cι-C2 alkoxy, amino, (di) (C1-C4) alkylamino and (poly)hydroxy (C2-C4) - alkylamino radicals; - R5, R6, R7, R8, Rii, R12, R13, i Riε and Rx7, which may be identical or different, represent a hydrogen atom, a (C1-C4) alkylsulphonyl or (C1-C4) alkyl-CO radical, a mono- or di (C1-C4) alkylcarboxamido radical, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, (C1-C4) alkylsulphonyl, (C1-C4)- alkylsulphonamido, carboxyl, mono- or (di) (C1-C4) alkylcarboxamido, (C1-C4) alkyl sulphoxide, amino, (di)(Cι-C4)- alkylamino or (poly)hydroxy(C2-C4) alkylamino; - R7 and R8 may also form,' with the nitrogen atom that bears them, a 5- to 8-membered ring optionally substituted with one or more radicals chosen from halogens and hydroxyl, Cι-C2 alkoxy, carboxyl, alkylsulphonamido and NRι3Ri4 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di(Cι~C4)- alkylcarboxamido or NR13R14;
X represents a hydrogen atom; a halogen atom; a C1-C4 alkoxy radical; a phenoxy radical optionally substituted with one or more radicals chosen from halogens and hydroxyl,, C1-C4 alkoxy, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, C1-C4 thioether, alkylsulphonamido, N i3Ri4 and C1-C4 alkyl radicals; a C1-C4 thioether radical optionally substituted with a hydroxyl, Cι-C2 alkoxy, carboxyl, sulphonic or amino radical, with the exception of the derivatives
Figure imgf000044_0001
2. Derivative according to Claim 1, in which Rl and R2 represent, independently of each other: - a hydrogen atom;
- a phenyl radical optionally substituted with one or more radicals chosen from halogens and hydroxyl, C1-C4 alkoxy, carboxyl, (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, C1-C4 thioether, alkylsulphonamido and Ri3Ri4 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di(Cι-C4)- alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NR13R14; - a linear or branched Ci-Cε alkyl radical optionally substituted with one or more hydroxyl, C1-C2 alkoxy, carboxyl, C1-C4 alkoxycarbonyl (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NR13R14 radicals.
3. Derivative according to Claim 2, in which Ri and R2, which may be identical or different, represent a hydrogen atom; a phenyl radical; a linear or branched C1-C4 alkyl radical, optionally substituted with one or more hydroxyl, Cι-C2 alkoxy, amino, di (C1-C4) alkylamino, carboxyl, (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonamido or NRι3Rι radicals in which Rι3 and R14, which may be identical or different, represent a hydrogen atom, a (C1-C4) alkyl-CO or a Cι-C2 alkyl radical optionally substituted with a hydroxyl or a Ci- C2 alkoxy.
4. Derivative according to Claim 3 , in which Ri and R2, which may be identical or different, represent a hydrogen atom, methyl, 2-hydroxyethyl, 2- carboxyethyl or 1, 2-dihydroxyethyl, or phenyl.
5. Derivative according to Claim 1, in which Ri and R2 form, with the nitrogen atom to which they are attached, a 5- to 8-membered heterocycle chosen from pyrrolidine, piperidine, homopiperidine, piperazine and homopiperazine, the said rings possibly being substituted with one or more radicals R4.
6. Derivative according to Claim 5 , in which Ri and R2 form, together with the nitrogen atom to which they are attached, a heterocycle chosen from pyrrolidine, 2 , 5-dimethylpyrrolidine, proline, 3- hydroxypro1ine, 4-hydroxyproline, 2,4- dicarboxypyrrolidine, 3-hydroxy-2- hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine, 2- ( iethy1- carboxamido)pyrrolidine, 2-hydroxymethylpyrrolidine, 3 , 4-dihydroxy-2-hydroxymethylpyrrolidine, 3-hydroxy- pyrrolidine, 3, 4-dihydroxypyrrolidine, 3-amino- pyrrolidine, 3-methylaminopyrrolidine, 4-amino-3- hydroxypyrrolidine, 3-hydroxy-4- (2-hydroxyethyl) - aminopyrrolidine, piperidine, 2 , 6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxa idopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethy1- piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxy- ho opiperidine, 2-carboxamidohomopiperidine, homo- piperazine, N-methylhomopiperazine and N-β-hydroxy- ethylhomopiperazine, and the addition salts thereof.
7. Derivative according to Claim 5 or 6, in which i and R2 form, together with the nitrogen atom to which they are attached, a heterocycle chosen from pyrrolidine, 3-hydroxypyrrolidine, 3-aminopyrrolidine, proline, 3-hydroxyproline, piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, homopiperidine, homopiperazine, N-methylhomopiperazine and N-β-hydroxyethylhomopiperazine, and the addition salts thereof.
8. Derivative according to any one of Claims 1 to 7, in which R3 represents a pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl or thienyl aromatic heterocycle.
9. Derivative according to Claims 1 to 8, in which R3 represents a radical RgS02NH- or a radical RιoC(0)NH-; with Rg and Rio, which may be identical or different, representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle such as pyridyl, pyrimidinyl, pyrazolyl, thiazolyl, furyl, imidazolyl or thienyl, these radicals being optionally substituted with one or more radicals chosen from halogens and hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido or NR11R12 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkyl- carboxamido or NR13R14 radicals; - a linear or branched Cι-C8 alkyl radical substituted with one or more radicals chosen from hydroxyl, Cι-C2 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, alkyl- sulphonamide and NRi6Rι7 radicals; - Rn, Rι , R13, Ri4, Ri6 and Rι , which may be identical or different, represent a hydrogen atom, acyl, a carboxamido or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, (C1-C4) alkylsulphonyl, (C1-C4) alkylsulphonamido, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (Cι-C4)alkyl sulphoxide, amino, (di) (C1-C4) alkylamino or (poly) hydroxy (C2-C4) alkylamino radicals .
10. Derivative according to Claim 9, in which R3 represents a radical RgS02NH- or a radical Ri0C(O)NH- with Rg and Rio which may be identical or different, chosen from an alkyl radical, a phenyl radical, a pyrazolyl, radical, a thiazolyl radical, a pyridyl radical and a thienyl radical, these radicals possibly being substituted.
11. Derivative according to Claim 10, in which R3 represents a radical Rι0C(0)NH- in which R10 represents a methyl, ethyl, 2-hydroxyethyl, 2-carboxyethyl, phenyl, pyrazolyl, thienyl or pyridyl radical and Rg represents a methyl, phenyl or tolyl radical.
12. Derivative- according to any one of
Claims 1 to 11, in which X represents a hydrogen atom, chlorine or an alkoxy radical.
13. Derivative according to any one of Claims 1 to 12, chosen from the following compounds, and the addition salts thereof with an acid or a base: 5-amino-2-methylsulphonylaminothiazole 5-amino-2-phenylsulphonylaminothiazole 5-amino-2-tolylsulphonylaminothiazole 5-amino-2-thiazolylsulphonylaminothiazole 5-amino-2-pyridylsulphonylaminothiazole 5-amino-2- (pyrid-2-yl) acylaminothiazole 5-amino-2- (pyrid-3-yl) acylaminothiazole 5-amino-2- (pyrid-4-yl) acylaminothiazole 5-amino-2-isopropylacylaminothiazole 5-amino-2- (thien-2-yl) acylaminothiazole
5-methylamino-2-methylsulphonylaminothiazole -methylamino-2-phenylsulphonylaminothiazole -methylamino-2-tolylsulphonylaminothiazole -methylamino-2-thiazolylsulphonylaminothiazole -methylamino-2-pyridylsulphonylaminothiazole -methylamino-2-phenacylaminothiazole
5-methylamino-2- (pyrid-2-yl) acylaminothiazole 5-methylamino-2- (pyrid-3-yl) acylaminothiazole 5-methylamino-2- (pyrid-4-yl).acylaminothiazole 5-methylamino-2-acetylaminothiazole 5-methylamino-2-isopropylacylaminothiazole
5-methylamino-2- (thien-2-yl) acylaminothiazole
5- (2-hydroxyethyl) amino-2-methylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-phenylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-tolylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-thiazolylsulphonylamino- thiazole
5- (2-hydroxyethyl)-amino-2-pyridylsulphonylaminothiazole 5- (2-hydroxyethyl) amino-2-phenacylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-2-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-3-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2- (pyrid-4-yl) acylaminothiazole 5- (2-hydroxyethyl) amino-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-2-isopropylacylaminothiazole 5- (2-hydroxyethyl) amino-2- (thien-2-yl) acylaminothiazole
5-amino-4-chloro-2-methylsulphonylaminothiazole 5-amino-4-chloro-2-phenylsulphonylaminothiazole 5-amino-4-chloro-2-tolylsulphonylaminothiazole 5-amino-4-chloro-2-thiazolylsulphonylaminothiazole 5-amino-4-chloro-2-pyridylsulphonylaminothiazole 5-amino-4-chloro-2-phenacylaminothiazole
5-amino-4-chloro-2- (pyrid-2-yl) acylaminothiazole 5-amino-4-chloro-2- (pyrid-3-yl) acylaminothiazole 5-amino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5-amino-4-chloro-2-acetylaminothiazole 5-amino-4-chloro-2-isopropylacylaminothiazole
5-amino-4-chloro-2- (thien-2-yl) acylaminothiazole
5-methylamino-4-chloro-2-methylsulphonylaminothiazole 5-methylamino-4-chloro-2-phenylsulphonylaminothiazole 5-methylamino-4-chloro-2-tolylsulphonylaminothiazole 5-methylamino-4-chloro-2-thiazolylsulphonylaird.no- thiazole 5-methylamino-4-chloro-2-pyridylsulphonylaminothiazole 5-methyl'amino-4-chloro-2-phenacylaminothiazole 5-methylamino-4-chloro-2- (pyrid-2-yl) acylaminothiazole 5-methylamino-4-chloro-2- (pyrid-3-yl) acylaminothiazole ' 5-methylamino-4-chloro-2- (pyrid-4-yl) acylaminothiazole 5-methylamino-4-chloro-2-acetylaminothiazole 5-methylamino-4-chloro-2-isopropylacylaminothiazole 5-methylamino-4-chloro-2- (thien-2-yl) acylaminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-methylsulphonyl- . aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-phenylsulphonyl- amiηothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-tolylsulphonyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-thiazolylsulphonyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-pyridylsulphonyl- aminothiazo1e 5- (2-hydroxyethyl) amino-4-chloro-2-phenacylaminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-2-yl) acyl- aminothiazo1e 5- (2-hydroxyethyl) amino-4-chloro-2- (pyrid-3-yl) acyl- aminothiazole
5- (2-Jιydroxyethyl) amino-4-chloro-2- (pyrid-4-yl) acylaminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2-acetylaminothiazole 5- (2-hydroxyethyl) amino-4-chloro-2-isopropylacyl- aminothiazole
5- (2-hydroxyethyl) amino-4-chloro-2- (thien-2-yl) acylaminothiazole
5- (pyrrolidin-1-yl) -2-methylsulphonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenylsulphonylaminothiazole 5- (pyrrolidin-1-yl) -2-tolylsulphonylaminothiazole 5- (pyrrolidin-1-yl) -2-thiazolylsulphonylaminothiazole 5- (pyrrolidin-1-yl) -2-pyridylsulphonylaminothiazole 5- (pyrrolidin-1-yl) -2-phenacylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-2-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2- (pyrid-3-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2- (ρyrid-4-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -2-acetylaminothiazole 5- (pyrrolidin-1-yl) -2-isopropylacylaminothiazole 5- (pyrrolidin-1-yl) -2- (thien-2-yl) acylaminothiazole
5- (pyrrolidin-1-yl) -4-chloro-2-methylsulphonylamino- thiazole
5- (pyrrolidin-1-yl) -4-chloro-2-phenylsulphonylamino- thiazole 5- (pyrrolidin-1-yl) -4-chloro-2-tolylsulphonylamino- thiazole
5- (pyrrolidin-1-yl) -4-chloro-2-thiazolylsulphonyl- aminothiazole
5- (pyrrolidin-1-yl) -4-chloro-2-pyridylsulphonylamino- thiazole 5- (pyrrolidin-1-yl) -4-chloro-2-phenacylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-2-yl) acylaminothiazole
5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-3-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2- (pyrid-4-yl) acylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-acetylaminothiazole 5- (pyrrolidin-1-yl) -4-chloro-2-isopropylacylaminothiazole
5- (pyrrolidin-1-yl) -4-chloro-2- (thien-2-yl) acylaminothiazole and also the addition salts thereof with an acid or a base.
14. Derivative according to any one of Claims 1 to 12, of formula (II)
Figure imgf000053_0001
in which R3 is as defined above in Claims 1 to 13.
15. Derivative according to any one of
Claims 1 to 14, chosen from 5- (pyrrolidin-1-yl) -2- (thien-2-yl) acylaminothiazole, and the addition salts thereof .
16. Composition for dyeing keratin fibres, comprising, in a medium that is suitable for dyeing:
- at least one oxidation base, and
- at least one thiazole derivative of formula (I) in which: • Ri and R2, which may be identical or different, represent: - a hydrogen atom; - a phenyl radical optionally substituted with one or more radicals chosen from halogens, hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, C1-C4 thioether, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido and NR13R14 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NRι3Ri4,-
- a linear or branched Cι-C8 alkyl radical optionally substituted with one or more hydroxyl, Cι-C2 alkoxy, carboxyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NRι3Ri4 radicals, - Ri and R2 may form, together with the nitrogen atom to which they are attached, a 5- to 8- membered heterocycle, one or more carbon atoms of the carbon-based ring of which may be replaced with an oxygen, nitrogen or sulphur atom or with an S02 group, the carbon atoms of the ring possibly being substituted with a radical R4 and the ring not comprising a peroxide bond or diazo or nitroso radicals;
- R4 represents : - a halogen atom; - a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, carboxyl, C1-C4 alkoxycarbonyl , C1-C4 alkoxy or NR5R6 radicals ; - a carboxyl radical; - a mono- or di (C1-C4) alkylcarboxamido radical; - a (C1-C4) alkylsulphonyl radical; - an alkylsulphonamido radical; - a hydroxyl radical; - a C1-C4 alkoxy radical; ' - a C2-C4 hydroxyalkoxy radical; - an aminosulphonyl radical; - a C1-C4 thioether radical; - a (C1-C4) alkyl sulphoxide radical; - a (C1-C4) alkylsulphonyl radical; - a radical NRR8; • R3 represents a radical RgS02NH- or a radical
Ri0C(O)NH- with Rg and Rio, which may be identical or different, representing: - a phenyl radical or a 5- or 6-membered aromatic heterocycle, these radicals optionally being substituted with one or more radicals chosen from halogens, hydroxyl, C1-C4 alkoxy, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, C1-C4 thioether, alkylsulphonamido or NR11R12 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di (C1-C4) alkyl- carboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, alkylsulphonamido or NRι3Ri4, - a linear or branched Cι-C8 alkyl radical optionally substituted with one or more hydroxyl, OR15, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, (C1-C4) alkyl sulphoxide, alkylsulphonamido or NR16R17 radicals; with R15 representing a C1-C4 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, QL-C2 alkoxy, amino, (di) (C1-C4) alkylamino and (poly)hydroxy (C2-C4) - alkylamino radicals;
- R5, R6, R7, R8, R11, R12, R13, Ri4, Rie and Ri7, which may be identical or different, represent a hydrogen atom, a
(C1-C4) alkylsulphonyl or (C1-C4) alkyl-CO radical, a mono- or di (C1-C4) alkylcarboxamido radical, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, (C1-C4) alkylsulphonyl, (C1-C4)- alkylsulphonamido, carboxyl, mono- or (di) (C1-C4) alkylcarboxamido, (C1-C4) alkyl sulphoxide, amino, (di)(Cι-C4)- alkylamino or (poly)hydroxy (C2-C4) alkylamino;
- R7 and R8 may also form, with the nitrogen atom that bears them, a 5- to 8-membered ring optionally substituted with one or more radicals chosen from halogens and hydroxyl, C-C2 alkoxy, carboxyl, alkylsulphonamido and NR13R14 radicals, or a C1-C4 alkyl radical optionally substituted with one or more hydroxyl, C1-C4 alkoxy, carboxyl, mono- or di(Cι-C4)- alkylcarboxamido or NR13R14;
X represents a hydrogen atom; a halogen atom; a C1-C4 alkoxy radical; a phenoxy radical optionally substituted with one or more radicals chosen from halogens and hydroxyl, C1-C4 alkoxy, carboxyl, C1-C4 alkoxycarbonyl, mono- or di (C1-C4) alkylcarboxamido, (C1-C4) alkylsulphonyl, sulphonic, alkyl sulphoxide, C1-C4 thioether, alkylsulphonamido, NRι3Ri4 and C1-C4 alkyl radicals; a C1-C4 thioether radical optionally substituted with a hydroxyl, Cι-C2 alkoxy, carboxyl, sulphonic or amino radical .
17. Composition according to Claim 16, in which the oxidation base(s) is (are) chosen from para- phenylenediamines, bis (phenyl) alkylenediamines, para- aminophenols, ortho-aminophenols and heterocyclic bases, and the addition salts thereof.
18. Composition according to either of Claims 16 and 17, in which the oxidation base(s) is (are) each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dye composition.
19. Composition according to any one of Claims 16 to 18, comprising one or more additional couplers chosen from meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers other than those of formula (I), and the addition salts thereof.
20. Composition according to any one of Claims 15 to 19, in which the coupler (s) is (are) each present in an amount of between 0.001% and 10% by weight relative to the total weight of the dye composition.
21. Process for the oxidation dyeing of keratin fibres, characterized in that a composition as defined in any one of Claims 16 to 20 is applied to the fibres in the presence of an oxidizing agent for a time that is sufficient to develop the desired colour.
22. Process according to Claim 21, in which the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes .
23. Process according to Claim 22, in which the oxidizing agent is mixed at the time of use with the composition as defined according to any one of Claims 16 to 19.
24. Process according to Claim 23, in which the oxidizing agent is applied to the fibres simultaneously with or sequentially to the composition as defined according to any one of Claims 16 to 19, in the form of an oxidizing composition.
25. Multi-compartment device, in which a first dye compartment contains a composition as defined in any one of Claims 16 to 19 and a second compartment contains an oxidizing agent.
26. Use of at least one thiazole derivative as defined according to any one of Claims 1 to 15, for the oxidation dyeing of keratin fibres.
27. Intermediate nitro derivatives of formula:
Figure imgf000059_0001
in which R9 and RIO are as defined in Claims 1 to 15.
PCT/EP2004/007994 2003-07-15 2004-06-25 2-acylamino or 2-sulfonylamino-1, 3-thiazoles as couplers for the oxidation dyeing of keratin fibres Ceased WO2005014591A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR0308606A FR2857664B1 (en) 2003-07-15 2003-07-15 NOVEL THIAZOLE DERIVATIVES AND USE OF THESE DERIVATIVES FOR DYEING KERATIN FIBERS
FR0308606 2003-07-15
US50711403P 2003-10-01 2003-10-01
US60/507,114 2003-10-01

Publications (1)

Publication Number Publication Date
WO2005014591A1 true WO2005014591A1 (en) 2005-02-17

Family

ID=34137700

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/007994 Ceased WO2005014591A1 (en) 2003-07-15 2004-06-25 2-acylamino or 2-sulfonylamino-1, 3-thiazoles as couplers for the oxidation dyeing of keratin fibres

Country Status (1)

Country Link
WO (1) WO2005014591A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1849785A1 (en) * 2006-04-28 2007-10-31 Neuropharma, S.A. N-(2-Thiazolyl)-amide derivatives as GSK-3 inhibitors
US7297168B2 (en) 2004-02-02 2007-11-20 The Procter & Gamble Company Keratin dyeing compounds, keratin dyeing compositions containing them, and use thereof
WO2015173324A1 (en) * 2014-05-16 2015-11-19 L'oreal Composition for dyeing keratin fibres, comprising an oxidation base and a particular heteroaryl coupler

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839523A (en) * 1955-04-01 1958-06-17 Eastman Kodak Co 2-amino-4-alkylsulfonyl-5-nitrothiazole azo compounds
US5071865A (en) * 1989-06-14 1991-12-10 Bayer Aktiengesellschaft Pesticidal 2-acylamino-4-halogeno-5-nitrothiazoles
US6114365A (en) * 1999-08-12 2000-09-05 Pharmacia & Upjohn S.P.A. Arylmethyl-carbonylamino-thiazole derivatives, process for their preparation, and their use as antitumor agents
WO2002057243A1 (en) * 2001-01-18 2002-07-25 Wella Aktiengesellschaft Novel 1,4-diamino-2-(thiazol-2-yl)benzene derivatives and dyes containing said compounds
EP1256578A1 (en) * 2001-05-11 2002-11-13 Pfizer Products Inc. Thiazole derivatives and their use as cdk inhibitors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839523A (en) * 1955-04-01 1958-06-17 Eastman Kodak Co 2-amino-4-alkylsulfonyl-5-nitrothiazole azo compounds
US5071865A (en) * 1989-06-14 1991-12-10 Bayer Aktiengesellschaft Pesticidal 2-acylamino-4-halogeno-5-nitrothiazoles
US6114365A (en) * 1999-08-12 2000-09-05 Pharmacia & Upjohn S.P.A. Arylmethyl-carbonylamino-thiazole derivatives, process for their preparation, and their use as antitumor agents
WO2002057243A1 (en) * 2001-01-18 2002-07-25 Wella Aktiengesellschaft Novel 1,4-diamino-2-(thiazol-2-yl)benzene derivatives and dyes containing said compounds
EP1256578A1 (en) * 2001-05-11 2002-11-13 Pfizer Products Inc. Thiazole derivatives and their use as cdk inhibitors

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BALQUIST, GOETZ: "a Re-investigation of the reaction between isothiocyanates and aminoacetonitrile", JOURNAL OF HETEROCYCLIC CHEMISTRY, vol. 9, 1972, pages 937 - 938, XP009024171 *
COOK ET AL: "studies in the azole series", JOURNAL OF CHEMICAL SOCIETY, 1948, pages 1262 - 1264, XP009024172 *
TAKAHASHI ET AL.: "synthesis of heterocyclic compounds of nitrogen.LXXXVI. 5-aminothiazole derivatives", YAKUGAKU ZASSHI, vol. 73, 1953, pages 1076, XP009024173 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7297168B2 (en) 2004-02-02 2007-11-20 The Procter & Gamble Company Keratin dyeing compounds, keratin dyeing compositions containing them, and use thereof
EP1849785A1 (en) * 2006-04-28 2007-10-31 Neuropharma, S.A. N-(2-Thiazolyl)-amide derivatives as GSK-3 inhibitors
WO2007125110A1 (en) * 2006-04-28 2007-11-08 Noscira, S.A. N- ( 2-thiazolyl) -amide derivatives as gsk-3 inhibitors
WO2015173324A1 (en) * 2014-05-16 2015-11-19 L'oreal Composition for dyeing keratin fibres, comprising an oxidation base and a particular heteroaryl coupler
FR3020945A1 (en) * 2014-05-16 2015-11-20 Oreal COMPOSITION FOR COLORING KERATINIC FIBERS COMPRISING AN OXIDATION BASE AND A PARTICULAR HETEROARYL COUPLER
US9993409B2 (en) 2014-05-16 2018-06-12 L'oreal Composition for dyeing keratin fibres, comprising an oxidation base and a particular heteroaryl coupler

Similar Documents

Publication Publication Date Title
KR100499191B1 (en) Compositions for dyeing keratinous fibres containing 3-amino pyrazolo-[1,5-a]-pyridines, dyeing method, novel 3-amino pyrazolo-[1,5-a]-pyridines
ES2254129T3 (en) CATIONIC OXIDATION BASES ITS USE FOR DYING BY OXIDATION OF KERATIN FIBERS, TINTORIAL COMPOSITIONS AND DYING PROCEDURES.
US7285137B2 (en) Composition for dyeing keratinous fibers comprising at least one diamino-N,N-dihydropyrazolone derivative
KR100339293B1 (en) Novel cationic 4-hydroxyindoles, their use for the oxidation dyeing of keratinous fibres, dyeing compositions, and methods of dyeing
WO2009098257A1 (en) Composition for dyeing keratin fibres comprising at least one cationic diamino-n,n-dihydropyrazolone derivative
US20040088799A1 (en) Oxidation dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in position 2
US20050097682A9 (en) Oxidation dyeing composition based on 1-(4-aminophenyl)pyrrolidines substituted in positions 2 and 4
FR2822689A1 (en) COMPOSITION FOR THE OXIDIZING DYE CONTAINING AT LEAST ONE 3-AMINO PYRAZOLO- [1,5-A] PYRIDINE OXIDIZATION BASE AND AT LEAST ONE 2-AMINO 3-HYDROXY PYRIDINE COUPLER
US6905522B2 (en) Dye composition comprising an oxidation base of the diaminopyrazole type, a cationic oxidation base and a coupler
US6939382B2 (en) 4, 5-diaminopyrazole derivatives in dimer form, and use thereof in the oxidation dyeing of keratin fibres
JP4071603B2 (en) A novel 2,5-diaminopyridine oxidation base for use in dyeing keratin fibers
WO2005014591A1 (en) 2-acylamino or 2-sulfonylamino-1, 3-thiazoles as couplers for the oxidation dyeing of keratin fibres
US20040074013A1 (en) Oxidation dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in positions 3 and 4, and dyeing method using same
JP4276131B2 (en) Novel imidazole compounds and use of these compounds for dyeing keratin fibers
KR20030068453A (en) Dye composition comprising an oxidation base of the diaminopyrazole type, a cationic oxidation base and a coupler
FR2857666A1 (en) TINCTORIAL COMPOSITION COMPRISING AS A COUPLER A FURANE DERIVATIVE AND NEW FURANE DERIVATIVES
US6579326B2 (en) Compositions for dyeing keratin fibers, containing cationic indolizine derivatives, and dyeing process
JP3719437B2 (en) Novel 6-alkoxy-2,3-diaminopyridine coupler useful for dyeing keratin fibers
US7238212B2 (en) Imidazole compounds and use of these compounds for dyeing keratinous fibers
US6916345B2 (en) 6-alkoxy-2,3-diaminopyridine couplers for dyeing keratin fibres
US7186277B2 (en) Composition for dyeing keratin fibres, comprising a cationic para-phenylenediamine derivative substituted with a diazacyclohexane or diazacycloheptane ring
FR2857664A1 (en) New thiazole derivatives and their addition salts used as couplers in hair dye compositions
WO2005068431A1 (en) Composition for dyeing keratin fibres, comprising at least one para-phenylenediamine derivative
US20040077852A1 (en) Para-phenylenediamine derivatives containing a pyrrolidyl group, and use of these derivatives for coloring keratin fibers
FR2850018A1 (en) TINCTORIAL COMPOSITION COMPRISING A PARTICULAR ACYLAMINOPHENOL COUPLER AND USE OF THIS COUPLER FOR DYING KERATIN FIBERS

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase