WO2019219932A1 - Para-phenylenediamine bases monosubstituted in position 2 with an oxy/thio-alkyl chain and use thereof for the oxidation dyeing of keratin fibres - Google Patents

Para-phenylenediamine bases monosubstituted in position 2 with an oxy/thio-alkyl chain and use thereof for the oxidation dyeing of keratin fibres Download PDF

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WO2019219932A1
WO2019219932A1 PCT/EP2019/062843 EP2019062843W WO2019219932A1 WO 2019219932 A1 WO2019219932 A1 WO 2019219932A1 EP 2019062843 W EP2019062843 W EP 2019062843W WO 2019219932 A1 WO2019219932 A1 WO 2019219932A1
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Aziz Fadli
Zhibo LIU
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L'oreal
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    • 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
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • 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
    • 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
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • 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
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • 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
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/24—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/29—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Definitions

  • the compounds of formula (I) or (II) denote compounds (1), (2), (3) and/or (4) as defined previously, in particular (1) and/or (2), and most particularly (1), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates.
  • the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
  • the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
  • ⁇ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from - 0-, -S-, -NH-, -S(O)-, -S(0) 2 -, -C(O)- and/or -C(S)-;
  • ALK is unsubstituted.
  • ALK represents an unsubstituted linear C 3 -C 6 alkylene chain; more preferentially unsubstituted linear C 3 -C 5 ; even more preferentially unsubstituted linear C 3 -C 4 ; better still unsubstituted linear C 3 such as propylene -(CH 2 ) 3 -.
  • R 2 represents:
  • ⁇ optionally substituted with one or more identical or different halogen atoms, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C 6 alkoxy, iii) acylamino, iv) amine -NH 2 , and v) aromatic or non-aromatic (hetero)cycle, such as phenyl; and/or ⁇ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0) 2 -, -C(O)- and/or -C(S)-.
  • radicals which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C 6 alkoxy, iii) acylamino, iv) amine -NH 2 , and v)
  • R 2 represents:
  • R 2 represents a hydroxyl radical, a methyl group, an ethyl group or an isopropyl group.
  • n represents an integer equal to 0 or 2.
  • the compound(s) of formula (III) are chosen from compounds (36) to (42) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
  • the compound(s) of formula (I) according to the invention are chosen from the compounds of formula (II) as described previously.
  • the compound(s) of formula (I) are chosen from compounds (1) to (42) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
  • the compounds of the invention are chosen from compounds 1, 2 and 12, more preferentially compound 1.
  • a subject of the invention is also the use of one or more compounds of formula (I), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, as an oxidation base for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
  • a subject of the invention is also the use of one or more compounds of formula (II), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, as an oxidation base for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
  • a subject of the invention is also the use of one or more compounds of formula (III), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, as an oxidation base for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
  • a subject of the invention is also a process for preparing the compounds of formula (II) as defined above, according to the following chemical synthetic scheme:
  • PG protecting group representing a protecting group which withstands the reaction conditions of the entire synthesis up to the deprotection step; the process consisting:
  • a first step i) in reducing the bicyclic amido derivative (a) to give the 4-nitroaniline compound substituted in alpha to the amino with a hydroxy- ALK group (b); preferably, this step is performed in a polar pro tic or aprotic organic solvent such as a (Ci-C 6 )alkanol, in particular methanol, or tetrahydrofuran (THF), in the presence of a reducing agent chosen in particular from borohydrides of an alkaline agent such as NaBH 4 ; and then, in a second step ii), in substituting the nucleofugal group LG of the reagent Ri-LG with compound (b), preferably in alkaline medium; and then, in a third step iii), in reducing the nitro compound (c) in particular by catalytic hydrogenation, preferably with palladium, nickel, zinc, iron, tin, preferably on graphite, such as Pd(II)/C, to give the compound
  • a second step ii) in protecting via a standard method for protecting an amine function in particular via a reagent such as R-C(Y a )-Y a -C(Y a )-R' with R and R', which may be identical or different, representing a (Ci-C 6 )alkyl group, and Y a , which may be identical or different, representing an oxygen or sulfur atom; preferably, said reagent is acetic anhydride; to give compound (c), and then, in a third step, in functionalizing the hydroxyl group with the nucleofugal LG of the reagent Ri-LG with compound (c), preferably in alkaline medium; and then, in a fourth step iv), in reacting the leaving group with a thiol compound R 2 -SH to give the nitro thiol compound (e), and compound (e) is then reduced in a step v) in particular by catalytic hydrogenation preferably with palladium, nickel, zinc
  • step vi) deprotected in step vi) to give compound (III-O) of the invention; or oxidized via a standard method in step vii) to give the sulfoxide compound (g), which is deprotected in step ix) to give the diamino sulfoxide compound (III- 1 ) according to the invention, or else said compound (g) is again oxidized in step viii) to give the sulfoxide compound (h), which is itself deprotected to give compound (III-2) of the invention.
  • composition (A) comprising, in a medium that is suitable for dyeing keratin fibres, in particular human keratin fibres such as the hair, one or more oxidation bases chosen from the compounds of formula (I), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, and mixtures thereof.
  • composition (A) has the same preferences and the same embodiments as the compounds of formula (II) according to the invention described previously.
  • the medium that is suitable for dyeing also known as the dye support, is cosmetically acceptable.
  • said medium generally comprises water or a mixture of water and of one or more solvents, for instance Ci-C 4 lower alkanols such as ethanol and isopropanol, polyols, for instance propylene glycol, dipropylene glycol or glycerol, and polyol ethers, for instance dipropylene glycol monomethyl ether.
  • the coupling agent(s) are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene -based couplers and heterocyclic couplers, the addition salts thereof, and mixtures thereof. More preferentially, the coupling agent(s) are chosen from 1,3- dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 4-chloro- 1 ,3-dihydroxybenzene,
  • para- phenylenediamine PPD
  • para-toluenediamine PTD
  • 2-chloro-l,4- phenylenediamine 2,3-dimethyl- 1 ,4-phenylenediamine, 2,6-dimethyl- 1 ,4- phenylenediamine, 2,6-diethyl- 1 ,4-phenylenediamine, 2,5-dimethyl- 1 ,4- phenylenediamine, N,N-dimethyl- 1 ,4-phenylenediamine, N,N -diethyl-para- phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3- methylaniline, N,N-bis(P-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(P-
  • heterocyclic bases mention may be made especially of pyridine, pyrimidine and pyrazole derivatives, and mixtures thereof.
  • pyridine oxidation bases that may be mentioned are the 3- aminopyrazolo[l,5-a]pyridine oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308.
  • Examples that may be mentioned include 2-acetylaminopyrazolo[l,5-a]pyrid-3-ylamine, 2-morpholin-4- ylpyrazolo[l,5-a]pyrid-3-ylamine, 2-methoxypyrazolo[l,5-a]pyrid-3-ylamine, (3- aminopyrazolo[l,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[l,5-a]pyrid-5- yl)ethanol, 2-(3-aminopyrazolo[l,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[l,5- a]pyrid-2-yl)methanol, 2-[(
  • the additional oxidation bases in the present invention may be chosen from 3-aminopyrazolo[l,5-a]pyridines and may preferably be substituted on carbon atom 2 with:
  • Ce- Cejalkyl groups such as a di(Ci-C 4 )alkylpiperazinium or imidazolium group
  • a (Ci-C 6 )alkoxy group optionally substituted with one or more hydroxyl groups, such as a b-hydroxyalkoxy group, and the corresponding addition salts.
  • the heterocyclic bases are chosen from the bases of formula (Va) in which R' represents a hydrogen atom or methyl, and R represents an ethyl, b- hydroxyethyl or «-hexyl group.
  • the heterocyclic bases are chosen from compounds (Val) to (Va4) below, and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates:
  • the total content of additional oxidation base(s) other than the compounds of formula (I) is between 0.001% and 10% by weight, more preferentially between 0.005% and 5% by weight, relative to the total weight of composition (A).

Abstract

The present invention relates to para-phenylenediamine compounds substituted in position 2 with an oxy/thio-alkyl chain. (Formula (I)) The present invention is used in the field of the dyeing of keratin fibres and more particularly the dyeing of keratin fibres, especially of human keratin fibres such as the hair.

Description

para-Phenylenediamine bases monosubstituted in position 2 with an oxy/thio- alkyl chain and use thereof for the oxidation dyeing of keratin fibres
The present invention relates to para-phenylenediamine compounds substituted in position 2 with an oxy/thio-alkyl chain.
The present invention is used in the field of the dyeing of keratin fibres and more particularly the dyeing of keratin fibres, especially of human keratin fibres such as the hair.
It is already known from the prior art that para-phenylenediamine bases play an important role in the process of hair dyeing. They are colourless or weakly coloured oxidation dye precursors which, in the presence of oxidizing compounds, are transformed into coloured compounds.
By combining an oxidation dye precursor with oxidizing compounds and dyeing couplers, a rich, broad range of colours is obtained.
"Permanent" dyeing is characterized by the use of dye precursors in the presence of oxidizing compounds. In order to be considered as efficient dyeing, said dyeing needs to satisfy certain criteria. It must make it possible to obtain shades in the desired intensity with colour differences, between the end and the root of a same lock (also known as the selectivity), which are as small as possible.
The colouring must also be resistant over time and must not become degraded in the presence of external agents such as washing, light, bad weather, rubbing and perspiration.
However, the dyeing results obtained are not always very satisfactory, especially in terms of colour build-up, selectivity, chromaticity, intensity and/or persistence in particular with respect to successive shampooing, or resistance to light or to perspiration.
There is thus a real need to propose colourings that have better dyeing properties, especially in terms of chromaticity, selectivity, power and fastness, and which are also capable of leading to a wide range of colours.
This aim is achieved by the present invention, one subject of which is especially a compound of formula (I) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000003_0001
in which formula (I):
• ALK represents a linear or branched alkylene chain including from 3 to 8 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy;
• X represents an oxygen atom -O- or a group S(0)n in which n represents an integer equal to 0, 1, or 2;
• R represents:
o a linear or branched (Ci-Cs)alkyl group:
■ optionally substituted with one or more halogen atoms, which may be identical or different, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, iii) (Ci-
C4)alkylcarbonyloxy such as acetyloxy, iv) acylamino, v) amino - NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-Cg)alkyl group, optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, S(O)-, -S(0)2-, -C(O)- and/or -C(S)-, and/or optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a Ci-C6 alkoxy radical, and vi) aromatic or non aromatic (hetero)cycle, such as phenyl; and/or
■ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from -O-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-; o a radical -CO-Ra in which Ra denotes a Ci-C6 alkyl radical optionally interrupted with an oxygen atom;
o or a hydroxyl radical when X represents a group S(0)n. These compounds make it possible to obtain better dyeing properties, and especially better solubility, colour build-up, chromaticity, fastness and selectivity. They also afford access to a wide range of light, natural and dark colours.
It has also been observed, surprisingly, that the keratin fibre colourings obtained with the compounds of the invention are particularly persistent with respect to external agents (washing, light, bad weather, friction, perspiration), and especially persistent for at least four shampoo washes.
The invention also relates to the use of one or more compounds of formula (I) for dyeing keratin fibres, in particular human keratin fibres such as the hair.
The present invention also relates to a composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising, in a suitable dyeing medium, one or more compounds of formula (I).
In particular, the invention relates to the use of said composition for dyeing keratin fibres, in particular human keratin fibres such as the hair.
The invention also relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising at least one step of applying to said fibres the dye composition according to the invention in the presence of one or more oxidizing agents for a time that is sufficient to obtain the desired colouring, after which the resulting fibres are rinsed, optionally washed with shampoo, rinsed again and dried or left to dry.
Another subject of the present invention concerns a multi-compartment dyeing device or kit comprising a first compartment containing a dye composition as described above and a second compartment containing one or more chemical oxidizing agents. The multi-compartment device is thus suitable for performing the dyeing process according to the invention.
Other characteristics, aspects, subjects and advantages of the present invention will emerge even more clearly on reading the description and the examples that follow.
For the purposes of the invention, unless otherwise indicated: - the limits of a range of values are included in that range, in particular in the expressions "between... and ..." and "ranging from ... to ...";
- the expression "at least one" used in the present description is equivalent to the expression "one or more", and may be replaced therewith;
- according to the present patent application, the term "keratin fibres" denotes human keratin fibres and more particularly the hair;
- the term "alkyl” denotes a linear or branched, saturated or unsaturated hydrocarbon-based group, comprising from 1 to 8 carbon atoms; preferably, the alkyl group is saturated, in particular, the alkyl group is a saturated Ci-C6 group such as methyl, ethyl, «-propyl, isopropyl, «- butyl, iso-butyl, /e/ -butyl, 2-butyl, «-pentyl, 2-pentyl, 3-pentyl or «- hexyl; more particularly, the alkyl group is a saturated linear Ci-C4 group such as methyl or ethyl;
- the term "alkoxy" denotes an alkyl-oxy group with alkyl as defined previously, preferably methoxy or ethoxy, or a cycloalkyloxy group such as a cycloprop yloxy group;
- the term "cycloalkyl" denotes a saturated or unsaturated cyclic hydrocarbon-based group, comprising from 3 to 8 carbon atoms; preferably, the cycloalkyl group is saturated, in particular, the cycloalkyl group is a saturated group comprising from 3 to 6 carbon atoms such as cyclopropyl;
- the term "alkylene" corresponds to a linear or branched divalent C3-C8 hydrocarbon-based group of general formula CnH2n with 3 < n < 8, in particular C3-C6; preferably C3-C4 such as propylene;
- the term "acylamino" corresponds to a group (-NR-C(O)-R') in which the radical R is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a Ci-C2 alkyl radical such as methyl;
- the term“( hetero)cycle” corresponds to an aromatic or non-aromatic, monocyclic or bicyclic, preferably monocyclic, 3- to lO-membered, preferably 3- to 8-membered, cyclic radical or heterocyclic radical, optionally substituted with one or more radicals, which may be identical or different, chosen from among the radicals: i) linear or branched C1-C4 alkyl; ii) hydroxyl; iii) C1-C4 alkoxy; iv) amino -NH2; one or more ring members of said“( hetero)cycle” possibly denoting a heteroatom such as O, S or N or a carbonyl diradical -CO-. It is understood that, for the purposes of the invention, a heterocyclic radical comprises one or more heteroatoms chosen, for example, from an oxygen atom, a nitrogen atom, a sulfur atom, optionally a nitrogen or oxygen atom, in particular a nitrogen atom.
For the purposes of the invention, the term“(hetero)cycle” preferably denotes a heterocyclic radical such as a pyrrolidinyl, piperidyl, morpholinyl, piperazinyl, pyrazolyl, imidazolyl or pyrrolidinone radical, said heterocyclic radical being optionally substituted with one or more
Ci-C4 alkyl radicals such as methyl;
- the term " addition salts of organic or mineral acids" more particularly means salts chosen from a salt derived from i) hydrochloric acid HC1, ii) hydrobromic acid HBr, iii) sulfuric acid H2S04, iv) alkylsulfonic acids: Alk-S(0)20H such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(0)20H such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-0-S(0)0H such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3C(0)0H; xiv) triflic acid CF3SO3H; and xv) tetrafluoroboric acid HBF4; preferably, the acid salts according to the invention are salts of mineral acids such as hydrochloric acid salts.
Compounds of formula (I)
One subject of the present invention relates to a compound of formula (I) below:
Figure imgf000006_0001
as defined previously.
Preferably, ALK is unsubstituted.
More preferentially, ALK represents an unsubstituted linear C3-C6 alkylene chain; even more preferentially unsubstituted linear C3-C5; better still unsubstituted linear C3-C4; or even unsubstituted linear C3 such as propylene -(CH2)3-.
Preferably, R3 and R4, which may be identical or different, represent a hydrogen atom or a linear (Ci-C4)alkyl group optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a Ci-C6 alkoxy radical.
More preferentially, R3 and R4, which may be identical or different, represent a hydrogen atom, a methyl group or an ethyl group. Preferably, n represents an integer equal to 0 or 2.
Preferably, a compound of formula (I) is chosen from the compounds of formula (II) or the compounds of formula (III) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000007_0001
in which formulae (II) and (III):
• ALK represents a linear or branched alkylene chain including from 3 to 8 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy;
• Ri represents:
o a linear or branched (Ci-Cs)alkyl group; ■ optionally substituted with one or more halogen atoms, which may be identical or different, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, iii) (Ci-C4)alkylcarbonyloxy such as acetyloxy, iv) acylamino, v) amino -NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-Cg)alkyl group, optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, - C(O)- and/or -C(S)-, and/or optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a Ci-C6 alkoxy radical, and vi) aromatic or non-aromatic (hetero)cycle, such as phenyl; and/or
■ optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-,
-S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
o a radical -CO-Ra in which Ra denotes a Ci-C6 alkyl radical optionally interrupted with an oxygen atom;
• R2 represents:
o a hydroxyl radical, or
o a linear or branched (C 1 -Cg)alkyl group;
■ optionally substituted with one or more identical or different halogen atoms, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, iii) acylamino, iv) amine -NH2, and v) aromatic or non-aromatic (hetero)cycle, such as phenyl, preferably aromatic or non- aromatic heterocycle; and/or
■ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from - O-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
• n represents an integer between 0 and 2. The compounds of formula (II)
According to a particular embodiment of the invention, the compound(s) of formula (I) are chosen from the compounds of formula (II) as defined previously, in particular chosen from those of formula (II) below:
Figure imgf000009_0001
in which formula (II):
• ALK represents a linear or branched alkylene chain including from 3 to 8 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) C i -C6 alkoxy;
• Ri represents:
a) a linear or branched (Ci-Cs)alkyl group:
■ optionally substituted with one or more halogen atoms, which may be identical or different, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) C i -C6 alkoxy, iii) (Ci-
C4)alkylcarbonyloxy such as acetyloxy, iv) acylamino, v) amino -NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-Cs)alkyl group, optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-, and/or optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a Ci-C6 alkoxy radical, and v) aromatic or non- aromatic (hetero)cycle, such as phenyl, preferably aromatic or non-aromatic heterocycle; and/or
■ optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
b) a radical -CO-Ra in which Ra denotes a C i -C6 alkyl radical optionally interrupted with an oxygen atom.
The addition salts with organic or mineral acids, the optical isomers, the geometrical isomers, the tautomers, and the solvates such as hydrates, of the compounds of formula (II) are also included in the subject of the invention.
Preferably, ALK is unsubstituted.
More preferentially, ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-.
Preferably, R3 and R4, which may be identical or different, represent a hydrogen atom or a linear (Ci-C4)alkyl group optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a Ci-C6 alkoxy radical.
More preferentially, R3 and R4, which may be identical or different, represent a hydrogen atom, a methyl group or an ethyl group.
According to an advantageous variant of the invention, the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
- ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-;
- R or, respectively, Rl represents
a) a linear or branched (Ci-Cg)alkyl group: ■ optionally substituted with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy such as methoxy or ethoxy or isoprop yloxy or cycloprop yloxy, iii) (Ci-C4)alkylcarbonyloxy such as acetyloxy, v) amino -NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group, and vi) aromatic or non aromatic heterocycle; and/or
■ optionally interrupted with one or more oxygen atoms;
b) a radical -CO-Ra in which Ra denotes a Ci-C6 alkyl radical optionally interrupted with an oxygen atom such as a methyl radical or a methoxymethylene radical.
According to a preferred embodiment of the invention, the compound(s) of formula (II) are chosen from compounds (1) to (35) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
According to a preferred embodiment of the invention, the compound(s) of formula (I) or (II) are chosen from compounds (1), (2) and/or (12), in particular (1) and/or (2), most particularly (1), as described previously, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates.
According to a particular embodiment of the invention, the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
- ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-, and/or
- R or, respectively, Ri represents a linear or branched (Ci-Cg)alkyl group, preferably a linear or branched (Ci-C6)alkyl group, more preferentially a linear or branched (Ci-C4)alkyl group, optionally substituted especially with one or more hydroxyl groups, and/or optionally interrupted with one or more oxygen atoms. Preferentially, R or, respectively, Ri represents a linear or branched (Ci-Cg)alkyl group, preferably a linear or branched (Ci-C6)alkyl group, more preferentially a linear or branched (Ci-C4)alkyl group.
According to this embodiment, the compounds of formula (I) or (II) denote compounds (1), (2), (3) and/or (4) as defined previously, in particular (1) and/or (2), and most particularly (1), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates. According to another particular embodiment of the invention, the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
- ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-;
- R or, respectively, Ri represents a linear or branched (Ci-Cg)alkyl group, substituted with a radical chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy such as methoxy or ethoxy or isoprop yloxy or cycloprop yloxy, iii) (Ci- C4)alkylcarbonyloxy such as acetyloxy, said alkyl radical being optionally interrupted with one or more oxygen atoms; preferably, Ri represents a linear or branched (C2-C3)alkyl group substituted with a radical chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy such as methoxy or ethoxy or isoprop yloxy or cyclopropyloxy, iii) (Ci-C4)alkylcarbonyloxy such as acetyloxy, said alkyl radical being optionally interrupted with one or more oxygen atom.
According to this embodiment, the compounds of formula (I) or (II) denote compounds (5), (6), (7), (8), (9), (10), (11), (25) and/or (26), as defined previously, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates.
According to another particular embodiment of the invention, the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
- ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-;
- R or, respectively, Ri represents a radical -CO-Ra in which Ra denotes a Ci-C6 alkyl radical optionally interrupted with an oxygen atom such as a methyl radical or a methoxymethylene radical.
According to one variant, R or Ri represents a radical -CO-Ra in which Ra denotes a Ci-C6 alkyl radical optionally interrupted with an oxygen atom, preferably not interrupted. According to this embodiment, the compounds of formula (I) or (II) denote compounds (12) and/or (13) as defined previously, in particular compound (12), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates.
According to another particular embodiment of the invention, the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
- ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-;
- R or, respectively, Ri represents a linear or branched (Ci-Cg)alkyl group substituted with v) an amino radical -NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group; in particular, Ri represents a linear or branched (C2-C3)alkyl group substituted with v) an amino radical -NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-C4)alkyl group. According to this embodiment, the compounds of formula (I) or (II) denote compounds (14), (15), (16), (27), (28), (29) and/or (30), as defined previously, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates.
According to an advantageous variant of the invention, the compounds of formula (I) denote the compounds of formula (I) or (II) for which:
- ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-;
- Ri represents a linear or branched (Ci-Cg)alkyl group substituted with vi) an aromatic or non-aromatic heterocycle, in particular a linear or branched (C2- C3)alkyl group substituted with vi) an aromatic or non- aromatic heterocycle. According to this embodiment, the compounds of formula (I) or (II) denote compounds (17), (18), (19), (20), (21), (22), (23), (24), (31), (32), (33), (34) or (35), as defined previously, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates.
The compounds of formula (III)
According to a particular embodiment of the invention, the compound(s) of formula (I) are chosen from the compounds of formula (III) as defined previously, in particular chosen from those of formula (III) below:
Figure imgf000019_0001
in which formula (III):
• ALK represents a linear or branched alkylene chain including from 3 to 8 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy;
• R2 represents:
o a hydroxyl radical, or
o a linear or branched (C i -C8)alkyl group;
■ optionally substituted with one or more identical or different halogen atoms, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, iii) acylamino, iv) amine -NH2, and v) aromatic or non-aromatic (hetero)cycle, such as phenyl; and/or
■ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from - 0-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
• n represents an integer between 0 and 2. According to the invention:
- the compounds of formula (III) for which n is equal to 0 are more particularly of formula (III-O) below:
Figure imgf000020_0001
- the compounds of formula (III) for which n is equal to 1 are more particularly of formula (III- 1 ) below:
Figure imgf000020_0002
- the compounds of formula (III) for which n is equal to 2 are more particularly of formula (III-2) below:
Figure imgf000020_0003
The groups ALK and R2 of the compounds of formula (III-O), (III- 1 ) or (III- 2) have the same definitions and the same preferences as the compounds of formula
(III). The addition salts with organic or mineral acids, the optical isomers, the geometrical isomers, the tautomers, and the solvates such as hydrates, of the compounds of formula (III), (III-O), (IP-l) and/or (III-2) are also included in the subject of the invention.
Preferably, ALK is unsubstituted.
More preferentially, ALK represents an unsubstituted linear C3-C6 alkylene chain; more preferentially unsubstituted linear C3-C5; even more preferentially unsubstituted linear C3-C4; better still unsubstituted linear C3 such as propylene -(CH2)3-.
Preferably, R2 represents:
o a hydroxyl radical, or
o a linear or branched (C 1 -C4)alkyl group;
■ optionally substituted with one or more identical or different halogen atoms, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, iii) acylamino, iv) amine -NH2, and v) aromatic or non-aromatic (hetero)cycle, such as phenyl; and/or ■ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-.
More preferentially, R2 represents:
o a hydroxyl radical, or
o a linear or branched (C 1 -C4)alkyl group.
Even more preferentially, R2 represents a hydroxyl radical, a methyl group, an ethyl group or an isopropyl group. Preferably, n represents an integer equal to 0 or 2.
According to a preferred embodiment of the invention, the compound(s) of formula (III) are chosen from compounds (36) to (42) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000022_0001
Figure imgf000023_0001
Preferably, the compound(s) of formula (I) according to the invention are chosen from the compounds of formula (II) as described previously.
According to a particularly preferred embodiment of the invention, the compound(s) of formula (I) are chosen from compounds (1) to (42) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
More particularly, the compounds of the invention are chosen from compounds 1, 2 and 12, more preferentially compound 1. A subject of the invention is also the use of one or more compounds of formula (I), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, as an oxidation base for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
A subject of the invention is also the use of one or more compounds of formula (II), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, as an oxidation base for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
A subject of the invention is also the use of one or more compounds of formula (III), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, as an oxidation base for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
Process for preparing the compounds of formula (II)
A subject of the invention is also a process for preparing the compounds of formula (II) as defined above, according to the following chemical synthetic scheme:
Figure imgf000030_0001
Figure imgf000030_0002
Deprotection
vii)
Figure imgf000030_0003
ill)
in which scheme:
Ri is as defined previously,
- ALK is as defined previously,
- ALK represents a linear or branched alkylene chain including from 2 to 7 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, LG (leaving group) represents a nucleofugal group such as halogen, tosyl or triflate,
PG (protecting group) representing a protecting group which withstands the reaction conditions of the entire synthesis up to the deprotection step; the process consisting:
* either, in a first step i), in reducing the bicyclic amido derivative (a) to give the 4-nitroaniline compound substituted in alpha to the amino with a hydroxy- ALK group (b); preferably, this step is performed in a polar pro tic or aprotic organic solvent such as a (Ci-C6)alkanol, in particular methanol, or tetrahydrofuran (THF), in the presence of a reducing agent chosen in particular from borohydrides of an alkaline agent such as NaBH4; and then, in a second step ii), in substituting the nucleofugal group LG of the reagent Ri-LG with compound (b), preferably in alkaline medium; and then, in a third step iii), in reducing the nitro compound (c) in particular by catalytic hydrogenation, preferably with palladium, nickel, zinc, iron, tin, preferably on graphite, such as Pd(II)/C, to give the compound of formula (II) of the invention;
* or, after the first step i), in a second step iv), in protecting the amino group of the 4-nitroaniline derivative substituted in alpha to the amino with a hydroxy- ALK group (b) with a protecting group in particular via a reagent such as R-C(Ya)-Ya- C(Ya)-R' with R and R', which may be identical or different, representing a (Ci- Cfjalkyl group, and Ya, which may be identical or different, representing an oxygen or sulfur atom; preferably, said reagent is acetic anhydride; to give compound (e); followed by steps v) and vi) of substitution and reduction under the same conditions as during steps ii) and iii) to give compounds (c) and of formula (II), respectively; and then, in a fifth step vii), compound (g) is deprotected, in particular in an organic solvent, preferably a polar protic organic solvent, more preferentially in the presence of one or more mineral or organic acids, more preferentially mineral acids such as hydrochloric acid, to give the compound of formula (II) as defined previously.
Process for preparing the compounds of formula (III)
Figure imgf000032_0001
in which scheme:
R2 is such as R2 defined previously, - ALK is as defined previously, ALK represents a linear or branched alkylene chain including from 2 to 7 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, - LG (leaving group) represents a nucleofugal group such as halogen, tosyl or triflate,
PG (protecting group) representing a protecting group which withstands the reaction conditions of the entire synthesis up to the deprotection step; the process for preparing the compounds of formula (III) consisting:
in a first step i) in reducing the bicyclic amido derivative (a) to give the 4- nitroaniline compound substituted in alpha to the amino with a hydroxy- ALK group (b); preferably, this step is performed in a polar pro tic or aprotic organic solvent such as a (Ci-C6)alkanol, in particular methanol, or tetrahydrofuran (THF), in the presence of a reducing agent chosen in particular from borohydrides of an alkaline agent such as NaBH4;
and then, in a second step ii), in protecting via a standard method for protecting an amine function in particular via a reagent such as R-C(Ya)-Ya-C(Ya)-R' with R and R', which may be identical or different, representing a (Ci-C6)alkyl group, and Ya, which may be identical or different, representing an oxygen or sulfur atom; preferably, said reagent is acetic anhydride; to give compound (c), and then, in a third step, in functionalizing the hydroxyl group with the nucleofugal LG of the reagent Ri-LG with compound (c), preferably in alkaline medium; and then, in a fourth step iv), in reacting the leaving group with a thiol compound R2-SH to give the nitro thiol compound (e), and compound (e) is then reduced in a step v) in particular by catalytic hydrogenation preferably with palladium, nickel, zinc, iron, tin, preferably on graphite, such as Pd(II)/C, to give the diamino compound of formula (f); which compound (f) is:
either deprotected in step vi) to give compound (III-O) of the invention; or oxidized via a standard method in step vii) to give the sulfoxide compound (g), which is deprotected in step ix) to give the diamino sulfoxide compound (III- 1 ) according to the invention, or else said compound (g) is again oxidized in step viii) to give the sulfoxide compound (h), which is itself deprotected to give compound (III-2) of the invention. Composition
Another subject of the present invention relates to a composition (A) comprising, in a medium that is suitable for dyeing keratin fibres, in particular human keratin fibres such as the hair, one or more oxidation bases chosen from the compounds of formula (I), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, and mixtures thereof.
The compound(s) of formula (I) present in composition (A) have the same preferences and the same embodiments as the compounds of formula (I) according to the invention described previously.
Preferably, the compound(s) of formula (I), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, are present in composition (A) according to the invention in a total content ranging from 0.1% to 20% by weight, more preferentially in a content ranging from 0.1% to 5% by weight relative to the total weight of composition (A). Preferably, composition (A) comprises, in a medium that is suitable for dyeing keratin fibres, in particular human keratin fibres such as the hair, one or more oxidation bases chosen from the compounds of formula (II) and/or the compounds of formula (III), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, and mixtures thereof.
The compound(s) of formula (II) optionally present in composition (A) have the same preferences and the same embodiments as the compounds of formula (II) according to the invention described previously.
Similarly, the compound(s) of formula (III) optionally present in composition (A) have the same preferences and the same embodiments as the compounds of formula (III) according to the invention described previously.
Preferably, the compound(s) of formula (II), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, are present in composition (A) according to the invention in a total content ranging from 0.1% to 20% by weight, more preferentially in a content ranging from 0.1% to 5% by weight relative to the total weight of composition (A).
Preferably, the compound(s) of formula (III), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, are present in composition (A) according to the invention in a total content ranging from 0.1% to 20% by weight, more preferentially in a content ranging from 0.1% to 5% by weight relative to the total weight of composition (A).
Preferably, the compound(s) of formula (II), and/or the compound(s) of formula (III), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined previously, are present in composition (A) according to the invention in a total content ranging from 0.1% to 20% by weight, more preferentially in a content ranging from 0.1% to 5% by weight relative to the total weight of composition (A).
The medium that is suitable for dyeing, also known as the dye support, is cosmetically acceptable. By way of example, said medium generally comprises water or a mixture of water and of one or more solvents, for instance Ci-C4 lower alkanols such as ethanol and isopropanol, polyols, for instance propylene glycol, dipropylene glycol or glycerol, and polyol ethers, for instance dipropylene glycol monomethyl ether.
The solvent(s) is (are) generally present in proportions that may be between 1% and 40% by weight approximately and even more preferably between 3% and
30% by weight approximately relative to the total weight of the dye composition.
For the purposes of the invention, the solvent(s) are in liquid form at room temperature (25°C) and at atmospheric pressure. Composition (A) according to the invention may optionally also comprise one or more coupling agents or "couplers".
Preferably, the coupling agent(s) are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene -based couplers and heterocyclic couplers, the addition salts thereof, and mixtures thereof. More preferentially, the coupling agent(s) are chosen from 1,3- dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 4-chloro- 1 ,3-dihydroxybenzene,
2.4-diamino- l-(P-hydroxyethyloxy)benzene, 2-amino-4-(P-hydroxyethylamino)-l- methoxybenzene, l,3-diaminobenzene, l,3-bis(2,4-diaminophenoxy)propane, 3- ureidoaniline, 3-ureido-l-dimethylaminobenzene, sesamol, 1 -b-hydroxyethylamino-
3.4-methylenedioxybenzene, a-naphthol, 2-methyl- l-naphthol, 6-hydroxyindole, 4- hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6- hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(b- hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bisf b- hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-
H-3-methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, 2,6- dimethylpyrazolo[ 1 ,5-b] - 1 ,2,4-triazole, 2,6-dimethyl[3,2-c] - 1 ,2,4-triazole, 6- methylpyrazolo[ 1 ,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(b- hydroxyethyl)amino-2-methylphenol, 3-aminophenol and 3-amino-2-chloro-6- methylphenol, the corresponding addition salts thereof with an acid and mixtures thereof.
Preferably, when the coupling agent(s) are present in composition (A), the total content of coupling agent(s) is between 0.001% and 10% by weight, more preferentially between 0.005% and 5% by weight, relative to the total weight of composition (A).
Composition (A) according to the invention may optionally also comprise one or more additional oxidation bases other than the compounds of formula (I) or (II) or (III) described previously.
Preferably, the additional oxidation base(s) other than the compounds of formula (I) or (II) or (III) described previously are chosen from para- phenylenediamines other than the compounds of formula (I) or (II) or (III) described previously, or from bis(phenyl)alkylenediamines, ortho-aminophenols, heterocyclic bases, the corresponding addition salts, and mixtures thereof.
Among the para-phenylenediamines other than the compounds of formula
(I) or (II) or (III) described previously, mention may be made especially of para- phenylenediamine (PPD), para-toluenediamine (PTD), 2-chloro-l,4- phenylenediamine, 2,3-dimethyl- 1 ,4-phenylenediamine, 2,6-dimethyl- 1 ,4- phenylenediamine, 2,6-diethyl- 1 ,4-phenylenediamine, 2,5-dimethyl- 1 ,4- phenylenediamine, N,N-dimethyl- 1 ,4-phenylenediamine, N,N -diethyl-para- phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3- methylaniline, N,N-bis(P-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(P- hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(P-hydroxyethyl)amino-2- chloroaniline, 2^-hydroxyethyl- 1 ,4-phenylenediamine, 2-methoxymethyl-l,4- phenylenediamine, 2-fluoro- 1 ,4-phenylenediamine, 2-isopropyl- 1 ,4- phenylenediamine, N-(P-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl - l,4-phenylenediamine, N,N-dimethyl-3-methyl-l,4-phenylenediamine, N-ethyl-N-(P- hydroxyethyl)-para-phenylenediamine, N-(P,y-dihydroxypropyl)-para- phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para- phenylenediamine, 2- b-hydroxyethyloxy- 1 ,4-phenylenediamine, 2- b- acetylaminoethyloxy- 1 ,4-phenylenediamine, N-^-methoxyethyl)-para- phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl- l,4-phenylenediamine, 2-b- hydroxyethylamino-5-aminotoluene and 3-hydroxy- 1 -(4'-aminophenyl)pyrrolidine, and the corresponding addition salts with an acid, and mixtures thereof.
More preferentially, the para-phenylenediamines other than the compounds of formula (I) or (II) or (III) described previously are chosen from PPD, PTD, N,N- bis^-hydroxyethyl)-para-phenylenediamine, 2^-hydroxyethyl- 1 ,4- phenylenediamine, 2-methoxyoxyethyl- 1 ,4-phenylenediamine, 2-isoprop yloxyethyl- l,4-phenylenediamine, 2-isopropyl-para-phenylenediamine, 2^-hydroxyethyloxy- para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para- phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2-chloro-para- phenylenediamine and 2-b-acetylaminoethyloxy-para-phenylenediamine, the corresponding addition salts thereof with an acid, and mixtures thereof.
Among the bis(phenyl)alkylenediamines, mention may be made especially of N,N'-bis^-hydroxyethyl)-N,N'-bis(4'-aminophenyl)- 1 ,3-diaminopropanol, N,N'- bis(b-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(b-hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine and 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, the corresponding addition salts, and mixtures thereof. Among the ortho-aminophenols, mention may be made especially of 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the corresponding addition salts, and mixtures thereof.
Among the heterocyclic bases, mention may be made especially of pyridine, pyrimidine and pyrazole derivatives, and mixtures thereof.
Other pyridine oxidation bases that may be mentioned are the 3- aminopyrazolo[l,5-a]pyridine oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308. Examples that may be mentioned include 2-acetylaminopyrazolo[l,5-a]pyrid-3-ylamine, 2-morpholin-4- ylpyrazolo[l,5-a]pyrid-3-ylamine, 2-methoxypyrazolo[l,5-a]pyrid-3-ylamine, (3- aminopyrazolo[l,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[l,5-a]pyrid-5- yl)ethanol, 2-(3-aminopyrazolo[l,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[l,5- a]pyrid-2-yl)methanol, 2-[(3-aminopyrazolo[l,5-a]pyrid-5-yl)(2-hydroxyethyl)- amino] ethanol, 2-[(3-aminopyrazolo[l,5-a]pyrid-7-yl)(2- hydroxyethyl)amino] ethanol, 3-aminopyrazolo[l,5-a]pyridin-5-ol, 3- aminopyrazolo[ 1 ,5-a]pyridin-4-ol, 3-aminopyrazolo[ 1 ,5-a]pyridin-6-ol, 3- aminopyrazolo[ 1 ,5-a]pyridin-7-ol, 2-b-hydroxyethoxy-3-aminopyrazolo[ 1 ,5- a]pyridine; 2-(4-dimethylpiperazinium-l-yl)-3-aminopyrazolo[l,5-a]pyridine, and the corresponding addition salts.
More particularly, the additional oxidation bases in the present invention may be chosen from 3-aminopyrazolo[l,5-a]pyridines and may preferably be substituted on carbon atom 2 with:
a) a (di)(Ci-C6)(alkyl)amino group, said alkyl group possibly being substituted with at least one hydroxyl, amino or imidazolium group;
b) an optionally cationic 5- to 7-membered heterocycloalkyl group containing from 1 to 3 heteroatoms, optionally substituted with one or more (Ci- Cejalkyl groups, such as a di(Ci-C4)alkylpiperazinium or imidazolium group; or c) a (Ci-C6)alkoxy group optionally substituted with one or more hydroxyl groups, such as a b-hydroxyalkoxy group, and the corresponding addition salts.
According to a particular embodiment of the invention, the additional oxidation bases other than the compounds of formula (I) described previously are chosen from pyrazoles and preferably 4,5-diaminopyrazoles optionally substituted in position 1 and/or 3 with a (Ci-Cio)alkyl, (poly)hydroxy(Ci-Cio)alkyl, (di)(Ci- C4)(alkyl)amino(Ci-Cio)alkyl or heterocyclo(Ci-Cio)alkyl group. In particular, the pyrazoles are chosen from the compounds of formula (Va) below:
Figure imgf000039_0001
and also the addition salts thereof with organic or mineral acids, the tautomers thereof, and the solvates thereof such as hydrates:
in which formula (Va):
• R represents a (Ci-Cio)alkyl group optionally substituted with one or more hydroxyl groups,
• R' represents a hydrogen atom or a (Ci-C4)alkyl group optionally substituted with a hydroxyl or amino group; preferably, R' represents a (Ci-C4)alkyl group such as methyl.
Preferably, the heterocyclic bases are chosen from the bases of formula (Va) in which R' represents a hydrogen atom or methyl, and R represents an ethyl, b- hydroxyethyl or «-hexyl group. The heterocyclic bases are chosen from compounds (Val) to (Va4) below, and also the organic or mineral acid salts thereof, and the solvates thereof such as hydrates:
Figure imgf000039_0002
(Val) (Va2) (Va3) (Va4)
Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP OS- 63124; EP 0770375 or patent application WO 96/15765, such as 2, 4,5,6- tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists, and mixtures thereof. Preferably, when the additional oxidation base(s) other than the compounds of formula (I) or (II) or (III) are present in composition (A), the total content of additional oxidation base(s) other than the compounds of formula (I) is between 0.001% and 10% by weight, more preferentially between 0.005% and 5% by weight, relative to the total weight of composition (A).
In general, the addition salts of the additional oxidation bases other than the compounds of formula (I) or (II) or (III) and coupling agents that may be used in the context of the invention are chosen in particular from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
Composition (A) according to the invention may also optionally comprise one or more direct dyes that may be chosen especially from nitrobenzene dyes, azo direct dyes, methine direct dyes, and mixtures thereof. These direct dyes may be of nonionic, anionic or cationic nature.
Preferably, when the direct dye(s) are present in composition (A), the total content of direct dye(s) is between 0.001% and 10% by weight, more preferentially between 0.005% and 5% by weight, relative to the total weight of composition (A).
Composition (A) according to the invention may optionally also comprise one or more chemical oxidizing agents.
The term " chemical oxidizing agent " means chemical oxidizing agents other than atmospheric oxygen.
Preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes (with the optional cofactors thereof) such as peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; preferentially, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, persalts, and mixtures thereof.
Preferably, when the chemical oxidizing agent(s) are present in composition (A), the total content of the chemical oxidizing agent(s) is between 1% and 50% by weight, more preferentially between 3% and 30% by weight, and even more preferentially between 5% and 20% by weight, relative to the total weight of composition (A).
Composition (A) according to the invention may also optionally comprise one or more adjuvants preferably chosen from anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers and/or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preservatives and opacifiers.
Preferably, when the above adjuvant(s) are present in composition (A), the adjuvant(s) are generally present in an amount, for each of them, of between 0.01% and 20% by weight, relative to the weight of composition (A).
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 (A) in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).
The pH of the dye composition (A) 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 in the dyeing of keratin fibres, or alternatively using standard buffer systems.
Among the acidifying agents that may be mentioned, by way of example, are mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid or sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
Among the basifying agents, examples that may be mentioned include aqueous ammonia, alkali metal carbonates, (Ci-C6)alkanolamines, such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (VI) below:
Figure imgf000042_0001
in which W is a (Ci-Cio)alkylene group such as propylene, optionally substituted with one or more hydroxyl groups; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.
The dye composition (A) with or without oxidizing agent 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, in particular human keratin fibres and especially the hair.
A subject of the invention is also the use of composition (A) as defined previously, for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair. Process for dyeing keratin fibres
Another subject of the present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising at least one step (i) of using on said keratin fibres a composition (A) as defined previously, optionally in the presence of a composition (B) containing one or more chemical oxidizing agents such as those described previously, different from composition (A).
Composition (A) as defined previously may be used in the presence simultaneously with or sequentially to a different composition (B) comprising one or more chemical oxidizing agents such as those described previously. According to a preferred embodiment of the invention, the process according to the invention is a process for dyeing keratin fibres, comprising at least one step (i) of applying to the keratin fibres a composition (M) resulting from the extemporaneous mixing of:
- a composition (A) as defined previously; and
- a different composition (B) comprising one or more chemical oxidizing agents. According to another preferred embodiment of the invention, the process according to the invention is a process for dyeing keratin fibres, comprising:
- at least one step (i) of applying to said keratin fibres a composition (A) as defined previously;
- at least one step (ii) of applying to said keratin fibres a different composition (B) comprising one or more chemical oxidizing agents; it being understood that steps (i) and (ii) of application to said keratin fibres are performed sequentially.
Preferably, according to this embodiment, step(s) (i) of application to the keratin fibres are performed before step(s) (ii).
For the purposes of the present invention, the term "sequentially" means that the composition (B) is applied before or after composition (A), i.e. as a pretreatment or a post-treatment. According to one variant of the invention, the process according to the invention is a process for dyeing keratin fibres, comprising:
- at least one step (i) of applying to said keratin fibres a composition (A) as defined previously;
- at least one step (ii) of applying to said keratin fibres a different composition (B) comprising one or more chemical oxidizing agents; it being understood that steps (i) and (ii) of application to said keratin fibres are performed simultaneously.
The embodiment according to which the keratin fibre treatment process according to the invention comprises at least one step (i) of applying to the keratin fibres a composition (M) resulting from the extemporaneous mixing of a composition (A) and of a different composition (B) is advantageously preferred.
The keratin fibre treatment process according to the present invention may optionally comprise additional steps, for example a step comprising a leave-on time after application and/or rinsing and/or drying.
The composition(s) may be applied to wet or dry hair, and preferably to wet or moist hair. The process of the invention may especially comprise a step of washing the hair before applying the composition(s) described previously. It may also comprise a washing step after the application of the composition(s) described previously.
According to one embodiment of the invention, the process consists in applying to the keratin fibres an effective amount of the composition(s) according to the invention, optionally massaging the fibres, optionally leaving the composition to stand on the fibres, and rinsing.
The leave-on time of composition(s) (A) and/or (B) and/or (M) on the keratin fibres may be between a few seconds and 60 minutes and preferably between 30 seconds and 30 minutes. The composition used in the keratin fibre treatment process according to the present invention is generally rinsed out with water.
An optional step of drying the keratin fibres may be performed.
Device
A subject of the invention is also a multi-compartment dyeing device or “kit” comprising:
- a first compartment containing a composition (A) according to the invention as defined previously; and
- a second compartment containing one or more chemical oxidizing agents as defined previously.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
EXAMPLES
Examples of synthesis
Example 1; synthesis of 2-(3-methoxypropyl)benzene-l, 4-diamine dihydrochloride
Figure imgf000045_0001
General synthetic scheme
Figure imgf000045_0002
8 g of 6-nitro-3,4-dihydroquinolin-2(lH)-one are placed in 40 mL of THF in a 250 mL three-necked flask under argon, equipped with a condenser, a thermometer and a magnetic bar. After cooling the medium <lO°C, 4.3 g of NaBH4 are added cautiously, the mixture is then heated to 45°C and 13.5 mL of methanol are added dropwise. After stirring for 45 minutes, the reaction is complete and the heating is switched off. 24 mL of water are added dropwise and the pH is then adjusted to pH 1-2 with diluted sulfuric acid solution while maintaining the temperature <40°C. The medium is then heated at 55°C for 3 hours, before evaporating off the THF under reduced pressure. The product precipitates out. The flask is placed in an ice bath and the pH is adjusted to pH>10. After heating for 1 hour at 30°C, the product is filtered off and then washed with water. The precipitate is dissolved in ethyl acetate and then heated at 55°C for 1 hour before filtering off the boron salts, evaporating the filtrate and drying the product in a desiccator. 3-(2-Amino-5-nitrophenyl)propan-l-ol is obtained in the form of a brown powder.
Figure imgf000046_0001
6.15 g of 3-(2-amino-5-nitrophenyl)propan-l-ol and 3.7 g of sodium tert- butoxide are placed in 50 mL of THF in a 100 mL three-necked flask equipped with a thermometer and a magnetic bar. After stirring for 10 minutes, 4 mL of dimethyl sulfate are added dropwise. After reaction for 4 hours at room temperature, water is added to the reaction medium and the THF is then stripped off under reduced pressure. Ethyl acetate is added and, after stirring and separation of the two phases, the aqueous phase is then extracted twice with ethyl acetate. The combined organic phases are washed twice with water and once with saturated sodium chloride solution. After drying over anhydrous magnesium sulfate, the organic phase is concentrated under reduced pressure. The brown oil thus obtained is purified on a column of silica, eluting with methanol/ethyl acetate (10/90), to give 2-(3- methoxypropyl)-4-nitroaniline.
Step 3:
Figure imgf000046_0002
A reduction is then performed with an H-cube on the 2-(3-methoxypropyl)- 4-nitroaniline obtained in step 2 under the following conditions:
Concentration: 0.05 mol/L in methanol, Pressure: 6.0 MPa (60 bar), Temperature: 70°C, Hydrogen production: 100%, Cartridge: 10% Pd/C, Flow rate: 3 mL/min.
After purification by precipitation from diisopropyl ether, 2- (3- methoxypropyl)benzene-l, 4-diamine dihydrochloride is obtained in the form of a white powder.
The NMR analyses are in accordance with the expected structure. Dyeing example
The dye compositions (Al) and (Bl) are prepared from the ingredients below:
Figure imgf000047_0001
Each composition (Al) and (Bl) obtained is applied to 1 g locks of natural Caucasian hair comprising 90% white hairs. After a leave-on time of 30 minutes at 27°C, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
The following colourings were obtained:
Figure imgf000047_0002
L, a, b results:
The colorimetric data for each of the locks are then measured with a Minolta
CM-36l0d spectrophotometer. In this L*a*b* system, L* represents the lightness, a* indicates the green/red colour axis and b* indicates the blue/yellow colour axis. The higher the value of L, the lighter or less intense the colour. Conversely, the lower the value of L, the darker or more intense the colour. The higher the value of a*, the redder the shade, and the higher the value of b*, the yellower the shade.
The colour build-up on hair thus corresponds to the variation in colouring between the locks of dyed NG hair (natural grey hair containing 90% white hairs) and the non-dyed (i.e. non-treated) NG hair, which is measured by (DE) according to the following equation:
Figure imgf000048_0001
In this equation, L*, a* and b* represent the values measured after dyeing of the NG hair, and Lo*, ao* and bo* represent the values measured before dyeing of the NG hair. The higher the DE value, the better the build-up of the colouring. The chromaticity is calculated according to the following formula:
C* = - /(a *)2 + (b*)2
The higher the chromaticity value C*, the more chromatic the colour of the treated keratin fibres.
Figure imgf000048_0002
It is seen from the results of the table that the keratin fibres dyed with the compounds of formula (I) according to the invention are dyed much more intensely and chromatically and with a better colour build-up than the fibres dyed with the hydroxylated comparative compound of composition (Al).

Claims

1. Compound of formula (I) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000050_0001
in which formula (I):
• ALK represents a linear or branched alkylene chain including from 3 to 8 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy;
• X represents an oxygen atom -O- or a group S(0)n in which n represents an integer equal to 0, 1, or 2;
• R represents:
o a linear or branched (Ci-Cs)alkyl group:
■ optionally substituted with one or more halogen atoms, which may be identical or different, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, iii) (Ci-
C4)alkylcarbonyloxy such as acetyloxy, iv) acylamino, v) amino - NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-Cg)alkyl group, optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, S(O)-, -S(0)2-, -C(O)- and/or -C(S)-, and/or optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a Ci-C6 alkoxy radical, and vi) aromatic or non aromatic (hetero)cycle, such as phenyl; and/or ■ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
o a radical -CO-Ra in which Ra denotes a C i -C6 alkyl radical optionally interrupted with an oxygen atom;
o or a hydroxyl radical when X represents a group S(0)n.
2. Compound according to the preceding claim, characterized in that it is chosen from the compounds of formula (II) or the compounds of formula (III) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000051_0001
in which formulae (II) and (III):
• ALK represents a linear or branched alkylene chain including from 3 to 8 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) C i -C6 alkoxy;
• Ri represents:
o a linear or branched (Ci-Cs)alkyl group;
■ optionally substituted with one or more halogen atoms, which may be identical or different, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) C i -C6 alkoxy, iii) (Ci-C4)alkylcarbonyloxy such as acetyloxy, iv) acylamino, v) amino -NR3R4 in which R3 and R4, which may be identical or different, represent a hydrogen atom or a linear or branched (Ci-Cg)alkyl group, optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, - C(O)- and/or -C(S)-, and/or optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a Ci-C6 alkoxy radical, and vi) aromatic or non-aromatic (hetero)cycle, such as phenyl; and/or
■ optionally interrupted with one or more additional heteroatoms and/or groups, which may be identical or different, chosen from -0-,
-S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
o a radical -CO-Ra in which Ra denotes a C i -C6 alkyl radical optionally interrupted with an oxygen atom;
• R2 represents:
o a hydroxyl radical, or
o a linear or branched (C i -C8)alkyl group;
■ optionally substituted with one or more identical or different halogen atoms, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) C i -C6 alkoxy, iii) acylamino, iv) amine -NH2, and v) aromatic or non-aromatic (hetero)cycle, such as phenyl, preferably aromatic or non- aromatic heterocycle; and/or
■ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
• n represents an integer between 0 and 2.
3. Compound according to either of the preceding claims, characterized in that ALK represents an unsubstituted linear C3-C6 alkylene chain, preferably unsubstituted linear C3-C5, more preferentially unsubstituted linear C3-C4, even more preferentially unsubstituted linear C3 such as propylene -(CH2)3-.
4. Compound according to any one of the preceding claims, characterized in that R3 and R4, which may be identical or different, represent a hydrogen atom or a linear (Ci-C4)alkyl group optionally substituted with one or more radicals, which may be identical or different, chosen from a hydroxyl radical, a C 1 -C6 alkoxy radical;
preferably, R3 and R4, which may be identical or different, represent a hydrogen atom, a methyl group or an ethyl group.
5. Compound according to any one of the preceding claims, characterized in that R or, respectively, Ri represents a linear or branched (Ci-Cg)alkyl group, preferably a linear or branched (Ci-C6)alkyl group, more preferentially a linear or branched (Ci-C4)alkyl group, optionally substituted especially with one or more hydroxyl groups, and/or optionally interrupted with one or more oxygen atoms; more preferentially, R or, respectively, Ri represents a linear or branched (Ci-Cg)alkyl group, preferably a linear or branched (Ci-C6)alkyl group, more preferentially a linear or branched (Ci-C4)alkyl group.
6. Compound according to any one of Claims 1 to 4, characterized in that R or Ri represents a radical -CO-Ra in which Ra denotes a Ci-C6 alkyl radical optionally interrupted with an oxygen atom, preferably not interrupted.
7. Compound according to any one of Claims 2 to 4, characterized in that R2 represents:
o a hydroxyl radical, or
o a linear or branched (C i -C4)alkyl group;
■ optionally substituted with one or more identical or different halogen atoms, and/or with one or more radicals, which may be identical or different, chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, iii) acylamino, iv) amine -NH2, and v) aromatic or non-aromatic (hetero)cycle, such as phenyl; and/or
■ optionally interrupted with one or more additional hetero atoms and/or groups, which may be identical or different, chosen from -0-, -S-, -NH-, -S(O)-, -S(0)2-, -C(O)- and/or -C(S)-;
preferably, R2 represents a hydroxyl radical, a methyl group, an ethyl group or an isopropyl group.
8. Compound according to any one of the preceding claims, characterized in that n represents an integer equal to 0 or 2.
9. Compound according to any one of the preceding claims, characterized in that it is chosen from compounds (1) to (42) below, and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates:
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
10. Compound according to any one of Claims 1 to 4 or 9, characterized in that it is chosen from compounds (1), (2) and/or (12) as defined according to Claim 9, in particular (1) and/or (2), most particularly (1), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates.
11. Use of one or more compounds of formula (I), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined according to any one of Claims 1 to 10, as an oxidation base for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair.
12. Composition (A) comprising, in a medium that is suitable for dyeing keratin fibres, in particular human keratin fibres such as the hair, one or more oxidation bases chosen from the compounds of formula (I), and also the addition salts thereof with organic or mineral acids, the optical isomers thereof, the tautomers thereof, and the solvates thereof such as hydrates, as defined according to any one of Claims 1 to 10, and mixtures thereof.
13. Composition according to the preceding claim, characterized in that it comprises one or more coupling agents chosen from meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, the addition salts thereof, and mixtures thereof; preferably, the coupling agent(s) are chosen from l,3-dihydroxybenzene, l,3-dihydroxy-2-methylbenzene, 4-chloro-l,3- dihydroxybenzene, 2,4-diamino- l-(P-hydroxyethyloxy)benzene, 2-amino-4-(P- hydroxyethylamino)-l-methoxybenzene, l,3-diaminobenzene, l,3-bis(2,4- diaminophenoxy)propane, 3-ureidoaniline, 3-ureido- 1 -dimethylaminobenzene, sesamol, l-P-hydroxyethylamino-3,4-methylenedioxybenzene, a-naphthol, 2-methyl- l-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino- 3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, l-N-(P-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(P- hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1- H-3-methylpyrazol-5-one, l-phenyl-3-methylpyrazol-5-one, 2,6- dimethylpyrazolo[ 1 ,5-b] - 1 ,2,4-triazole, 2,6-dimethyl[3,2-c] - 1 ,2,4-triazole, 6- methylpyrazolo[ 1 ,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(b- hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 3-amino-2-chloro-6- methylphenol, the corresponding addition salts thereof with an acid, and mixtures thereof.
14. Composition according to either of Claims 12 and 13, characterized in that it comprises one or more chemical oxidizing agents; preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids, and oxidase enzymes (with the possible cofactors thereof), for instance peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases, and mixtures thereof; more preferentially, the chemical oxidizing agent(s) are chosen from hydrogen peroxide and persalts, and mixtures thereof.
15. Process for dyeing keratin fibres, in particular human keratin fibres such as the hair, characterized in that it comprises at least one step (i) of using on said keratin fibres a composition (A) as defined according to any one of Claims 12 to 14, optionally in the presence of a different composition (B) containing one or more chemical oxidizing agents as defined according to Claim 14.
16. Process for dyeing keratin fibres according to the preceding claim, characterized in that it comprises at least one step (i) of applying to the keratin fibres a composition (M) resulting from the extemporaneous mixing of:
- a composition (A) as defined according to either of Claims 12 and 13; and
- a different composition (B) comprising one or more chemical oxidizing agents as defined according to Claim 14.
17. Process for dyeing keratin fibres according to Claim 15, characterized in that it comprises:
- at least one step (i) of applying to said keratin fibres a composition (A) as defined according to either of Claims 12 and 13;
- at least one step (ii) of applying to said keratin fibres a different composition (B) comprising one or more chemical oxidizing agents as defined according to Claim 14;
it being understood that steps (i) and (ii) of application to said keratin fibres are performed simultaneously or sequentially; preferably, the step(s) (i) are performed before the step(s) (ii).
18. Process for preparing the compounds of formula (II) as defined according to any one of Claims 2 to 10, according to the following chemical synthetic scheme:
Figure imgf000062_0001
Figure imgf000062_0002
in which scheme:
- Ri is as defined in any one of Claims 2, 5 and 6;
- ALK is as defined in any one of Claims 1 to 3;
ALK represents a linear or branched alkylene chain including from 2 to 7 carbon atoms, optionally substituted with one or more identical or different halogen atoms, and/or with one or more identical or different radicals chosen from among the radicals: i) hydroxyl, ii) Ci-C6 alkoxy, LG (leaving group) representing a nucleofugal group such as halogen, tosyl or triflate, PG (protecting group) representing a protecting group which withstands the reaction conditions of the entire synthesis up to the deprotection step; the process consisting:
* either, in a first step i), in reducing the bicyclic amido derivative (a) to give the 4-nitroaniline compound substituted in alpha to the amino with a hydroxy- ALK group (b); preferably, this step is performed in a polar pro tic or aprotic organic solvent such as a (Ci-C6)alkanol, in particular methanol, or tetrahydrofuran (THF), in the presence of a reducing agent chosen in particular from borohydrides of an alkaline agent such as NaBH4; and then, in a second step ii), in substituting the nucleofugal group LG of the reagent Ri-LG with the compound (b), preferably in alkaline medium; and then, in a third step iii), in reducing the nitro compound (c) in particular by catalytic hydrogenation preferably with palladium, nickel, zinc, iron, tin, preferably on graphite, such as Pd(II)/C, to give the compound of formula (II) as defined according to any one of Claims 2 to 10;
* or, after the first step i), in a second step iv), in protecting the amino group of the 4-nitroaniline derivative substituted in alpha to the amino with a hydroxy- ALK group (b) with a protecting group in particular via a reagent such as R-C(Ya)-Ya- C(Ya)-R' with R and R', which may be identical or different, representing a (Ci- Cfjalkyl group, and Ya, which may be identical or different, representing an oxygen or sulfur atom; preferably, said reagent is acetic anhydride; to give compound (e); followed by steps v) and vi) of substitution and reduction under the same conditions as during steps ii) and iii) to give compounds (c) and of formula (II), respectively; and then, in a fifth step vii), compound (g) is deprotected, in particular in an organic solvent, preferably a polar protic organic solvent, more preferentially in the presence of one or more mineral or organic acids, more preferentially mineral acids such as hydrochloric acid, to give the compound of formula (II) as defined according to any one of Claims 2 to 10.
19. Process for preparing the compounds of formula (III) as defined according to any one of Claims 2 to 10, according to the following chemical synthetic scheme:
Figure imgf000064_0001
in which scheme:
R2 is such as R2 defined in Claim 2 or 7 ;
- ALK is as defined in any one of Claims 1 to 3;
- ALK- 1 , LG and PG are as defined in the preceding claim; the process consisting: in a first step i) in reducing the bicyclic amido derivative (a) to give the 4-nitroaniline compound substituted in alpha to the amino with a hydroxy- ALK group (b); preferably, this step is performed in a polar protic or aprotic organic solvent such as a (Ci-C6)alkanol, in particular methanol, or tetrahydrofuran (THF), in the presence of a reducing agent chosen in particular from borohydrides of an alkaline agent such as NaBH4;
and then, in a second step ii), in protecting via a standard method for protecting an amine function in particular via a reagent such as R-C(Ya)-Ya-C(Ya)-R' with R and R', which may be identical or different, representing a (Ci-C6)alkyl group, and Ya, which may be identical or different, representing an oxygen or sulfur atom; preferably, said reagent is acetic anhydride; to give compound (c), and then, in a third step, in functionalizing the hydroxyl group with the nucleofugal LG of the reagent Ri-LG with compound (c), preferably in alkaline medium; and then, in a fourth step iv), in reacting the leaving group with a thiol compound R2-SH to give the nitro thiol compound (e), and compound (e) is then reduced in a step v) in particular by catalytic hydrogenation preferably with palladium, nickel, zinc, iron, tin, preferably on graphite, such as Pd(II)/C, to give the diamino compound of formula (f); which compound (f) is:
either deprotected in step vi) to give compound (III-O) of the invention; - or oxidized via a standard method in step vii) to give the sulfoxide compound (g), which is deprotected in step ix) to give the diamino sulfoxide compound (III- 1 ) according to the invention, or else said compound (g) is again oxidized in step viii) to give the sulfoxide compound (h), which is itself deprotected to give compound (III-2) of the invention.
20. Multi-compartment dyeing device or "kit" comprising:
a first compartment containing a composition as defined according to either of Claims 12 and 13; and
- a second compartment containing one or more chemical oxidizing agents as defined according to Claim 14.
PCT/EP2019/062843 2018-05-17 2019-05-17 Para-phenylenediamine bases monosubstituted in position 2 with an oxy/thio-alkyl chain and use thereof for the oxidation dyeing of keratin fibres WO2019219932A1 (en)

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