[go: up one dir, main page]

WO2008034650A1 - Composition de coloration de fibres de keratine comprenant un colorant direct diazoique cationique contenant une unite 2-imidazolium - Google Patents

Composition de coloration de fibres de keratine comprenant un colorant direct diazoique cationique contenant une unite 2-imidazolium Download PDF

Info

Publication number
WO2008034650A1
WO2008034650A1 PCT/EP2007/055241 EP2007055241W WO2008034650A1 WO 2008034650 A1 WO2008034650 A1 WO 2008034650A1 EP 2007055241 W EP2007055241 W EP 2007055241W WO 2008034650 A1 WO2008034650 A1 WO 2008034650A1
Authority
WO
WIPO (PCT)
Prior art keywords
radical
radicals
alkyl
represent
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2007/055241
Other languages
English (en)
Inventor
Andrew Greaves
Hervé David
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LOreal SA filed Critical LOreal SA
Priority to EP07857191A priority Critical patent/EP2032540A1/fr
Priority to US12/302,658 priority patent/US20100031453A1/en
Publication of WO2008034650A1 publication Critical patent/WO2008034650A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with 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
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems

Definitions

  • the present invention relates to a composition for dyeing keratin fibres, and in particular human keratin fibres such as the hair, comprising at least one cationic diazo direct dye containing a 2-imidazolium unit .
  • these dyes are applied to the fibres, optionally in the presence of an oxidizing agent, if it is desired to obtain simultaneous lightening of the fibres.
  • an oxidizing agent if it is desired to obtain simultaneous lightening of the fibres.
  • the colorations resulting from the use of direct dyes are temporary or semi-permanent colorations since the nature of the interactions that bind the direct dyes to the keratin fibre, and their desorption from the surface and/or core of the fibre, are responsible for their low dyeing power and their poor relative fastness to washing or perspiration.
  • Certain direct dyes may be unstable under standard lightening dyeing conditions and/or they have insufficient photostability properties.
  • the aim of the present invention is to provide direct dyes that do not have the drawbacks of the existing direct dyes.
  • one of the aims of the present invention is to provide blue or violet direct dyes, which are stable in oxidizing medium or light-stable, which make it possible to obtain colorations that are resistant over time with respect to external attacking factors such as light, bad weather, washing, perspiration and rubbing.
  • composition for dyeing keratin fibres comprising, in a suitable dyeing medium, at least one cationic diazo direct dye containing a 2-imidazolium unit, chosen from the compounds of formula (I) or (II) below, the mesomeric forms thereof, and also the acid-addition salts thereof, and the solvates thereof:
  • radicals Ri represent, independently of each other : - a linear or branched, saturated, acyclic, optionally substituted Ci-C 8 hydrocarbon-based chain, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen or sulfur, CO, SO and SO 2 , or combinations thereof; the hydrocarbon-based chain not comprising any nitro, nitroso, peroxo or diazo functions and being necessarily attached to the quaternized or non-quaternized nitrogen atom of the imidazolium ring via a carbon atom; an optionally substituted phenyl radical; an optionally substituted benzyl radical;
  • radicals R 2 represent, independently of each other: a linear Ci-C 4 alkyl radical, optionally substituted with an amino radical or a hydroxyl radical; an optionally substituted phenyl radical; - a halogen atom;
  • the radicals R 3 represent, independently of each other : a linear Ci-C 4 alkyl radical, optionally substituted with an amino radical or a hydroxyl radical; a hydroxyl radical; a Ci-C 4 alkoxy radical; a Ci-C 4 monohydroxyalkoxy or polyhydroxyalkoxy radical; - an amino radical optionally substituted with one or two Ci-C 4 alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl radical; a group R a CO-NR a '- in which the radical R a represents a Ci-C 4 alkyl radical; the radical R a ' represents a hydrogen atom or a Ci-C 4 alkyl radical;
  • radicals Rb represent, independently of each other, a hydrogen atom or a Ci-C 4 alkyl radical
  • a halogen atom preferably chlorine or fluorine
  • the radicals R 4 represent, independently of each other: a linear Ci-C 4 alkyl radical; a hydroxyl radical; a Ci-C 4 alkoxy radical;
  • Ci-C 4 alkyl radicals an amino radical optionally substituted with one or two Ci-C 4 alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl radical; the two alkyl radicals possibly forming, together with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle optionally comprising another heteroatom identical to or different from nitrogen, such as a pyrrolidine, morpholine or piperidine ring, optionally substituted with one or more methyl, hydroxyl, amino, monomethylamino or dimethylamino radicals; a group R a CO-NR a '- in which the radical R a represents a Ci-C 4 alkyl radical; the radical R a ' represents a hydrogen atom or a Ci-C 4 alkyl radical;
  • radicals Rb represent, independently of each other, a hydrogen atom or a Ci-C 4 alkyl radical
  • R c group (R c ) 2N-CO-NR 0 - in which the radicals R c represent, independently of each other, a hydrogen atom or a Ci-C 4 alkyl radical
  • Rd group (Rd) 2N-SO2- in which the radicals Rd represent, independently of each other, a hydrogen atom or a Ci-C 4 alkyl radical
  • cyano radical a halogen atom, preferably chlorine or fluorine
  • the radicals R 5 and R 6 which may be identical or different, represent: a hydrogen atom; a linear or branched, saturated, acyclic, optionally substituted
  • o is an integer equal to 0 or 1; - Rx and Ry represent, independently of each other, a hydrogen atom or a methyl radical; the radicals R5 and R 6 possibly forming, with the nitrogen atom to which they are attached and each with a radical R 4 located ortho to the group NR 5 R 6 , an optionally substituted 5- or 6-membered heterocycle of formula (IV) below:
  • o is an integer equal to 0 or 1;
  • Rx and Ry represent, independently of each other, a hydrogen atom or a methyl radical
  • n is an integer between 0 and 2; when n is less than 2, the unsubstituted carbon atom(s) bear(s) a hydrogen atom;
  • n' is an integer between 0 and 4 and preferably between 0 and 2; when n' is less than 4, the unsubstituted carbon atom(s) bear(s) a hydrogen atom;
  • n is an integer between 0 and 4 and preferably between 0 and 3; when n" is less than 4, the unsubstituted carbon atom(s) bear(s) a hydrogen atom; the electrical neutrality of the compounds of formula (I) or (II) being assured by one or more identical or different cosmetically acceptable anions An.
  • a subject of the present invention is also a process for dyeing keratin fibres using the composition in accordance with the present invention.
  • a subject of the present invention is also a multi ⁇ compartment device for performing the process in accordance with the invention.
  • a subject of the present invention is also the use for dyeing keratin fibres of the composition in accordance with the invention.
  • a subject of the present invention is also novel cationic diazo direct dyes.
  • the present invention allows the production of colorations that are resistant to the various attacking factors to which the hair may be subjected, and especially to shampooing.
  • the present invention also allows blue or violet colorations to be obtained, especially sparingly chromatic blue colorations, which lead to fundamental and/or natural shades.
  • the direct dyes used in the context of the invention are light-stable and stable under standard lightening dyeing conditions, in particular in the presence of an oxidizing agent and/or of ammonia.
  • an alkyl radical or the alkyl part of a radical is linear or branched; an alkyl radical or the alkyl part of the radical is said to be substituted when it comprises at least one substituent chosen from the following groups : • hydroxyl;
  • Ci-Ci 6 and preferably Ci-C 8 alkyl radical optionally substituted with one or more radicals chosen from the following radicals: hydroxyl, C1-C2 alkoxy, C1-C4 monohydroxyalkoxy or polyhydroxyalkoxy, Ci-C 4 alkylcarbonylamino, amino substituted with two Ci-C 4 alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl radical, the two radicals possibly forming, with the nitrogen atom to which they are attached, a 5- to 7-membered and preferably 5- or 6-membered heterocycle, optionally comprising another heteroatom that is identical to or different from nitrogen;
  • halogen atom such as chlorine, fluorine or bromine
  • Ci-C 2 alkoxy radical • a Ci-C 4 monohydroxyalkoxy or polyhydroxyalkoxy radical;
  • Ci-C 4 alkyl radicals which may be identical or different, optionally bearing at least one hydroxyl or amino radical substituted with two optionally substituted Ci-C 2 alkyl radicals;
  • Ci-C 4 alkoxy Ci-C 4 monohydroxyalkoxy or poly- hydroxyalkoxy .
  • the radicals Ri are chosen from a Ci-C 4 alkyl radical, optionally ending with a hydroxyl.
  • the radicals Ri represent a methyl radical, an ethyl radical or a 2-hydroxyethyl radical.
  • n is equal to 0 or the radicals R 2 are chosen from a Ci-C 4 alkyl radical optionally substituted with an amino radical or a hydroxyl radical.
  • the radicals R 2 are chosen from a methyl radical; an ethyl radical; a 2-hydroxyethyl radical; a 3-aminopropyl radical.
  • the radicals R 3 are chosen from a Ci-C 4 alkyl radical; a Ci-C 4 alkoxy radical; a halogen atom; an optionally substituted amino radical; a group R a CO-NR a ' - in which the radical R a represents a Ci-C 4 alkyl radical; the radical R a ' represents a hydrogen atom; a hydroxyl radical.
  • the radicals R 3 are chosen from a methyl radical; a methoxy radical; a chlorine atom; a hydroxyl radical; a methylcarbonyl- amino radical.
  • the radicals R 4 are chosen from an alkyl radical; a hydroxyl radical; an alkoxy radical; a Ci-C 4 mono (alkyl) amino or di (alkyl) amino radical; a Ci-C 4 di (hydroxyalkyl) amino radical; a halogen atom; a group R a C0-NR a ' - in which the radical R a represents a Ci-C 4 alkyl radical and the radical R a ' represents a hydrogen atom.
  • the radicals R 4 are chosen from a methyl radical; a hydroxyl radical; an ethyl- amino radical; a dimethylamino radical; a bis (2- hydroxyethyl) amino radical; a chlorine atom; a methyl- carbonylamino radical.
  • the radicals R5 and R 6 which may be identical or different, represent: a Ci-C 4 alkyl radical, optionally substituted with at least one hydroxyl radical; - a benzyl radical optionally substituted with one or more hydroxyl and/or amino radicals.
  • the radicals R 5 and R 6 form, together with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 7-membered heterocycle, optionally comprising another heteroatom, which may be identical to or different from nitrogen, for instance a pyrrolidine, piperazine, homo- piperazine or piperidine nucleus.
  • one of the radicals R 5 or R 6 forms, with the nitrogen atom to which it is attached and with a radical R 4 located ortho to the group NR 5 R 6 , an optionally substituted 5- or 6-membered heterocycle of formula (III) below: in which: o is an integer equal to 0 or 1; - Rx and Ry represent, independently of each other, a hydrogen atom or a methyl radical.
  • rings of formula [III) mention may be made of the following rings:
  • radicals R5 and R 6 form, with the nitrogen atom to which they are attached and each with a radical R 4 located ortho to the group NR 5 R 6 , an optionally substituted 5- or 6-membered heterocycle of formula (IV) below:
  • 0 is an integer equal to 0 or 1; - Rx and Ry, independently of each other, represent a hydrogen atom or a methyl radical.
  • rings of formula (IV) mention may be made of the following rings:
  • An represents an organic or mineral anion or mixture of anions, which makes it possible to balance the charge (s) on the compounds of formula (I) or (II), chosen, for example, from a halide such as a chloride, bromide, fluoride or iodide ion; a hydroxide; a sulfate; a hydrogen sulfate; an alkyl sulfate for which the linear or branched alkyl part is of Ci-C 6 , for instance the methyl sulfate or ethyl sulfate ion; carbonates and hydrogen carbonates; carboxylic acid salts such as formate, acetate, citrate, tartrate or oxalate; alkylsulfonates for which the linear or branched alkyl part is of Ci-C 6 , for instance the methylsulfonate ion; arylsulfonates for which the aryl part,
  • the acid-addition salts of the compounds of formula (I) or (II) may be, for example, the addition salts with an organic or mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid or (alkyl- or phenyl-) sulfonic acids such as p-toluenesulfonic acid or methylsulfonic acid.
  • organic or mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid or (alkyl- or phenyl-) sulfonic acids such as p-toluenesulfonic acid or methylsulfonic acid.
  • the solvates of the compounds of formula (I) or (II) represent the hydrates of such compounds and/or the combination of a compound of formula (I) or (II) with a linear or branched C1-C4 alcohol such as methanol, ethanol, isopropanol or n-propanol.
  • the direct dyes of formula (I) or (II) are preferably chosen from the direct dyes of formula (I') or (II') below:
  • radicals R' i represent, independently of each other, a Ci-C 4 alkyl radical; a 2-hydroxyethyl radical; • the radicals R' 3 represent, independently of each other, a Ci-C 4 alkyl radical; a C x -C 4 alkoxy radical; a halogen atom; a hydroxyl radical; a methylcarbonylamino radical;
  • m' represents an integer equal to 0, 1 or 2; • the radicals R' 4 represent, independently of each other, a Ci-C 4 alkyl radical; a hydroxyl radical; an alkoxy radical; a mono (alkyl) amino or di (alkyl) amino radical; a di (hydroxyalkyl) amino radical; a halogen atom such as chlorine; a (Ci- C 4 ) alkylcarbonylamino radical;
  • • m" represents an integer equal to 0, 1, 2 or 3; • the radicals R' 5 and R' 6 represent, independently of each other, a Ci-C 4 alkyl radical; a Ci-C 4 mono- hydroxyalkyl radical; or form, with one or two radicals R' 4 located ortho to the group NR' 5 R' 6 and the benzene nucleus to which they are attached, a ring of formula (III) or (IV) .
  • the direct dyes of formula (I) or (II) that are useful in the context of the invention may be prepared, for example, according to the synthetic mode as described in patent US 3 173 907 and detailed below.
  • the direct dyes of formula (I) or (II) that are useful in the context of the invention may also be prepared according to the synthetic modes as described below.
  • the diazotization reaction of an aromatic amine takes place in the presence of a diazotization reagent such as sodium nitrite in acidic medium (a mineral acid such as hydrochloric acid or orthophosphoric acid or an organic acid such as acetic acid) .
  • a diazotization reagent such as sodium nitrite in acidic medium (a mineral acid such as hydrochloric acid or orthophosphoric acid or an organic acid such as acetic acid) .
  • acidic medium a mineral acid such as hydrochloric acid or orthophosphoric acid or an organic acid such as acetic acid
  • Other reagents may be more suitable if the diazonium salt under consideration is unstable in aqueous medium; examples that will be mentioned include alkyl nitrites, such as amyl nitrite, or nitrosylsulfuric acid. These reagents are formal equivalents of nitrous acid.
  • the diazonium salt may be used in the following step directly (use of the reaction mixture) , after having been isolated (for example by precipitation and vacuum filtration) or after modification of the characteristics of the mixture (modification of pH, dilution, concentration, addition of a solvent other than the initial solvent) .
  • the excess diazotization reagents used during the first step may be destroyed at the end of the operation by adding sulfamic acid or urea to the reaction medium.
  • the step that consists in reacting the diazonium salt obtained beforehand with an aromatic amine (or an imidazole or derivatives thereof) is possible either by pouring a solution of the latter reagent into the solution of diazonium salt as obtained after the first step (or by redissolving the isolated diazonium salt) , or, conversely, by pouring the solution of diazonium salt into the solution of the aromatic amine (or of the imidazole or derivatives thereof) .
  • the pH of the reaction medium is adjusted by adding a base since the "coupling" reaction normally takes place at a pH higher than that of the diazotization step.
  • the base may be introduced into the reaction medium before, but preferably at the same time or after, the placing in contact of the aromatic amine and the diazonium salt.
  • This sequence of two reactions leads to the formation of an azo compound.
  • the diazotization reaction is preferably performed in an acidified polar (a)protic solvent, such as water acidified with hydrochloric acid, acetic acid or sulfuric acid, where appropriate in the presence of a cosolvent such as ethyl alcohol, THF or dioxane, at a pH below 6.
  • the temperature is less than 4O 0 C and preferably less than 15 0 C.
  • the reaction time is between one minute and twentyfour hours .
  • the coupling of the diazonium salt thus formed and of the aromatic amine may take place in the same solvent, to which a cosolvent may be added, the pH possibly being raised by adding an organic or mineral base such as sodium hydroxide to the reaction medium.
  • the temperature is maintained below 4O 0 C and preferably below 15 0 C.
  • the reaction takes place in a time of between one minute and twentyfour hours .
  • the alkylation step is performed with an alkylating reagent such as an alkyl sulfate, an alkyl halide, an alkyl alkylsulfonate or an alkyl arylsulfonate . It is also possible to use an oxirane to perform this alkylation .
  • an alkylating reagent such as an alkyl sulfate, an alkyl halide, an alkyl alkylsulfonate or an alkyl arylsulfonate . It is also possible to use an oxirane to perform this alkylation .
  • the alkylation reaction takes place, for example, in a halogenated solvent, for example dichloromethane or 1, 2-dichloroethane, or an ester, for example ethyl acetate, at a temperature below 15O 0 C, preferably at the reflux point of the solvent, in the presence of a mineral base (MgO, K 2 CO 3 , Na 2 CO 3 , etc.) or an organic salt (Na + OAc " , etc. ) .
  • a halogenated solvent for example dichloromethane or 1, 2-dichloroethane, or an ester, for example ethyl acetate
  • the cationic dyes precipitate in apolar solvents, which allows them to be isolated and purified.
  • the direct dye(s) used in the context of the invention generally represent (s) from 0.01% to 5% by weight relative to the total weight of the composition and more particularly from 0.05% to 2% by weight relative to the total weight of the composition.
  • composition according to the invention may also comprise an oxidation base.
  • This oxidation base may be chosen from the oxidation bases conventionally used in oxidation dyeing, for example para-phenylenediamines, bis (phenyl) alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases.
  • para-phenylenediamines that may be mentioned more particularly are, for example, para-phenylene- diamine, para-tolylenediamine, 2-chloro-para- phenylenediamine, 2, 3-dimethyl-para-phenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2, 6-diethyl-para- phenylenediamine, 2, 5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para- phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N,N-bis ( ⁇ -hydroxy- ethyl) -para-phenylenediamine, 4-N, N-bis ( ⁇ -hydroxy- ethyl) amino-2-methylaniline, 4-N, N-bis ( ⁇ -hydroxyethyl
  • para-phenylenediamine para-tolylenediamine, 2-isopropyl- para-phenylenediamine, 2- ⁇ -hydroxyethyl-para-phenylene- diamine, 2- ⁇ -hydroxyethyloxy-para-phenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2, 6-diethyl-para- phenylenediamine, 2, 3-dimethyl-para-phenylenediamine, N,N-bis ( ⁇ -hydroxyethyl) -para-phenylenediamine, 2-chloro-para-phenylenediamine and 2- ⁇ -acetylamino- ethyloxy-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.
  • the bis (phenyl) alkylenediamines that may be mentioned, for example, are N, N' -bis ( ⁇ -hydroxyethyl) - N, N' -bis (4' -aminophenyl) -1, 3-diaminopropanol, N, N' -bis- ( ⁇ -hydroxyethyl) -N, N' -bis (4 ' -aminophenyl) ethylene- diamine, N, N' -bis (4-aminophenyl) tetramethylenediamine, N, N' -bis ( ⁇ -hydroxyethyl) -N, N' -bis (4-aminophenyl) tetra- methylenediamine, N, N' -bis (4-methylaminophenyl) tetra ⁇ methylenediamine, N, N' -bis (ethyl) -N, N' -bis (4 ' -amino-3' - methylphen
  • para-aminophenols that may be mentioned, for example, are para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethyl- phenol, 4-amino-2- ( ⁇ -hydroxyethylaminomethyl) phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.
  • ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
  • heterocyclic bases for example, are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and derivatives of pyrazolo [ 1, 2-a] pyrazol-1-one type.
  • pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino- pyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 2, 3-diamino-6-methoxypyridine, 2- ( ⁇ -methoxyethyl) amino- 3-amino-6-methoxypyridine and 3, 4-diaminopyridine, and the addition salts thereof with an acid.
  • pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2 359 399; JP 88-169 571; JP 05-163 124; EP 0 770 375 or patent application WO 96/15765, such as 2,4,5, 6-tetraaminopyrimidine, 4-hydroxy-2, 5, 6-triamino- pyrimidine, 2-hydroxy-4, 5, 6-triaminopyrimidine, 2,4- dihydroxy-5, 6-diaminopyrimidine and 2, 5, 6-triamino ⁇ pyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo [ 1, 5- a] pyrimidine-3, 7-diamine; 2, 5-dimethylpyrazolo [1,5- a] pyrimidine-3, 7-diamine; pyrazolo [ 1, 5-a] pyrimidine- 3, 5-diamine; 2, 7-di
  • pyrazole derivatives that may be mentioned are the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4, 5-diamino-l-methylpyrazole, 4, 5-diamino-l- ( ⁇ -hydroxy- ethyl) pyrazole, 3, 4-diaminopyrazole, 4, 5-diamino-l- (4' - chlorobenzyl) pyrazole, 4, 5-diamino-l, 3-dimethy1- pyrazole, 4, 5-diamino-3-methyl-l-phenylpyrazole, 4,5- diamino-l-methyl-3-phenylpyrazole, 4-amino-l, 3- dimethyl-5-hydrazinopyrazole, l-benzyl-4, 5-diamino- 3-methylpyrazole, 4, 5-
  • composition according to the invention may also contain one or more couplers conventionally used for dyeing keratin fibres.
  • couplers conventionally used for dyeing keratin fibres.
  • couplers mention may be made especially of meta-phenylenediamines, meta- aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers.
  • Examples that may be mentioned include 2-methyl- 5-aminophenol, 5-N- ( ⁇ -hydroxyethyl) amino-2-methyl- phenol, 6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1, 3-dihydroxybenzene, 1, 3-dihydroxy-2-methylbenzene, 4-chloro-l, 3-dihydroxybenzene, 2, 4-diamino-l- ( ⁇ - hydroxyethyloxy) benzene, 2-amino-4- ( ⁇ -hydroxyethyl- amino) -1-methoxybenzene, 1, 3-diaminobenzene, 1,3- bis (2 , 4-diaminophenoxy) propane, 3-ureidoaniline, 3- ureido-1-dimethylaminobenzene, sesamol, 1- ⁇ -hydroxy- ethylamino-3, 4-methylenedioxybenzene, ⁇ -naphthol, 2- methyl-1-naphthol, 6-hydroxyindole
  • the oxidation base(s) is (are) generally present in an amount ranging from 0.001% to 10% by weight, and more preferably from 0.005% to 6% by weight, relative to the total weight of the dye composition.
  • the coupler (s) is
  • the acid-addition salts that may be used in the context of the dye compositions of the invention for the oxidation bases and couplers are chosen especially from the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.
  • composition according to the invention may optionally comprise at least one additional direct dye other than the compounds of formula (I) or (II) .
  • This dye may be chosen from cationic and nonionic species.
  • Non-limiting examples that may be mentioned include nitrobenzene dyes, azo, azomethine, methine, tetraazapentamethine, anthraquinone, naphthoquinone, benzoquinone, phenothiazine, indigoid, xanthene, phenanthridine, phthalocyanin and triarylmethane-based dyes and natural dyes, alone or as mixtures.
  • nitrobenzene dyes azo, azomethine, methine, tetraazapentamethine, anthraquinone, naphthoquinone, benzoquinone, phenothiazine, indigoid, xanthene, phenanthridine, phthalocyanin and triarylmethane-based dyes and natural dyes, alone or as mixtures.
  • red or orange nitrobenzene dyes l-hydroxy-3-nitro-4-N- ( ⁇ -hydroxypropyl) aminobenzene, - N- ( ⁇ -hydroxyethyl) amino-3-nitro-4-aminobenzene, l-amino-3-methyl-4-N- ( ⁇ -hydroxyethyl) amino-6-nitro- benzene, l-hydroxy-3-nitro-4-N- ( ⁇ -hydroxyethyl) aminobenzene, 1, 4-diamino-2-nitrobenzene, - l-amino-2-nitro-4-methylaminobenzene,
  • the additional direct dye may also be chosen from yellow and green-yellow nitrobenzene direct dyes; mention may be made, for example, of the compounds chosen from: - l- ⁇ -hydroxyethyloxy-3-methylamino-4-nitrobenzene, l-methylamino-2-nitro-5- ( ⁇ , ⁇ -dihydroxypropyl) oxy- benzene,
  • R B represents a Ci-C 4 alkyl radical or a ⁇ -hydroxy ⁇ ethyl, ⁇ -hydroxypropyl or ⁇ -hydroxypropyl radical;
  • R A and R 0 which may be identical or different, represent a ⁇ -hydroxyethyl, ⁇ -hydroxypropyl, ⁇ -hydroxy- propyl or ⁇ , ⁇ -dihydroxypropyl radical, at least one of the radicals R B , Rc or R A representing a ⁇ -hydroxypropyl radical and R B and R 0 not simultaneously being able to denote a ⁇ -hydroxyethyl radical when R B is a ⁇ -hydroxy- propyl radical, such as those described in French patent FR 2 692 572.
  • azo direct dyes that may also be mentioned are the following dyes described in the Colour Index International 3rd edition:
  • azine dyes that may be mentioned are the following compounds:
  • indoamine dyes that may be used according to the invention, mention may be made of the following compounds:
  • the medium that is suitable for dyeing also known as the dye support, generally consists of water or of a mixture of water and of at least one organic solvent to dissolve the compounds that are not sufficiently water- soluble.
  • the organic solvents are chosen from linear or branched, preferably saturated monoalcohols or diols containing from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2- methyl-2 , 4-pentanediol) , neopentyl glycol and 3-methyl- 1, 5-pentanediol; aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; glycols or glycol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ether, propylene glycol and its ethers, for instance propylene glycol monomethyl ether, butylene glycol and dipropylene glycol; and also diethylene glycol alkyl ethers, especially of Ci-C 4 , for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
  • aromatic alcohols such as benzyl alcohol and
  • the usual solvents described above, when they are present, usually represent from 1% to 40% by weight and more preferably from 5% to 30% by weight relative to the total weight of the composition.
  • the dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric associative polymeric thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance silicones, which may or may not be volatile or modified, film-forming agents, ceramides, preserving agents and opacifiers.
  • adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic poly
  • the above adjuvants are generally present in an amount for each of them of between 0.01% and 20% by weight relative to the weight of the composition.
  • the pH of the dye composition in accordance with the invention is generally between about 3 and 12 and preferably between about 5 and 11. It may be adjusted to the desired value using acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.
  • W is a propylene residue optionally substituted with a hydroxyl group or a Ci-C 4 alkyl radical
  • R n , RE ⁇ RF and R G which may be identical or different, represent a hydrogen atom, a Ci-C 4 alkyl radical or a Ci-C 4 hydroxyalkyl radical.
  • the dye composition according to the invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair.
  • composition according to the invention may also comprise at least one oxidizing agent to allow simultaneous lightening.
  • the oxidizing agent When the oxidizing agent is present, it may be added to the composition comprising the compound (s) of formula (I) at the time of use, or may be applied directly to the keratin fibre.
  • a solution of sodium nitrite (0.108 g) dissolved in water (1 mL) is added dropwise to the product obtained previously (0.509 g) predissolved in 5N hydrochloric acid (3 mL) and acetonitrile (8 mL) , while maintaining a temperature of less than 5 0 C.
  • a solution of sodium nitrite (0.113 g) dissolved in water (13 mL) is added dropwise to the product obtained in the preceding step (0.45 g) dissolved in 5N hydrochloric acid (36.5 mL) and acetonitrile (11.5 mL) , while maintaining the reaction medium at a temperature below 5 0 C.
  • step 3 The product obtained in step 3 (233 mg) is dissolved in THF (50 mL) in the presence of sodium acetate (60 mg) . Dimethyl sulfate (174 mg) is added and the reaction mixture is then stirred at 65 0 C for two hours. The reaction medium is then concentrated by distilling off the solvents under vacuum, and the residue thus obtained is purified by chromatography on silica-60 gel, using the dichloromethane/methanol binary mixture as eluent. 215 mg of product are thus obtained. A second purification step consists in reslurrying the product in heptane for 45 minutes. After filtration and then drying under vacuum, 150 mg of pure product are obtained. The analyses indicate that the expected product has indeed been obtained (NMR, HPLC) .
  • Aqueous ammonia containing 20% NH 3 2.94 g For the colorations performed under non-lightening conditions (without oxidizing agent) , these compositions are applied directly to the hair.
  • an oxidizing medium is used for the colorations performed under lightening conditions.
  • each composition is mixed with an equal weight of 20-volumes aqueous hydrogen peroxide solution (6% by weight) .
  • a final pH equal to 7 and to 9.5, respectively, is obtained.
  • composition with or without oxidizing agent is applied to locks of grey hair containing 90% white hairs, at a rate of 6 g of composition per 1 g of hair. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
  • the locks thus dyed are subjected to a wash-fastness test, which consists in shampooing 12 times (with a standard shampoo) and evaluating the colour after these 12 shampoo washes. After 12 shampoo washes, the locks are still coloured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne une composition de coloration de fibres de kératine, contenant au moins un colorant direct diazoïque cationique choisi parmi les composés de formule (I) ou (II) ci-dessous, les formes mésomèriques de ceux-ci, ainsi que les solvates et les sels d'addition acide de ceux-ci. La présente invention permet de produire des colorations résistantes aux divers facteurs d'agression auxquels les cheveux peuvent être soumis, en particulier lors du shampooinage. L'invention permet également d'obtenir des colorations bleues ou violettes, notamment des colorations bleues légèrement chromatiques, ce qui permet d'obtenir des tons fondamentaux et/ou naturels. Les colorants directs utilisés dans la présente invention sont également résistants à la lumière et stables dans des conditions de coloration éclaircissante normales, en particulier en présence d'un oxydant et/ou d'ammoniac.
PCT/EP2007/055241 2006-06-01 2007-05-30 Composition de coloration de fibres de keratine comprenant un colorant direct diazoique cationique contenant une unite 2-imidazolium Ceased WO2008034650A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP07857191A EP2032540A1 (fr) 2006-06-01 2007-05-30 Composition de coloration de fibres de keratine comprenant un colorant direct diazoique cationique contenant une unite 2-imidazolium
US12/302,658 US20100031453A1 (en) 2006-06-01 2007-05-30 Composition for dyeing keratin fibres, comprising a cationic diazo direct dye containing a 2-imidazolium unit

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR0652004A FR2901794A1 (fr) 2006-06-01 2006-06-01 Composition pour la coloration des fibres keratiniques comprenant un colorant direct diazoique a motif 2-imidazolium
FR0652004 2006-06-01
US81488106P 2006-06-20 2006-06-20
US60/814,881 2006-06-20

Publications (1)

Publication Number Publication Date
WO2008034650A1 true WO2008034650A1 (fr) 2008-03-27

Family

ID=37685259

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/055241 Ceased WO2008034650A1 (fr) 2006-06-01 2007-05-30 Composition de coloration de fibres de keratine comprenant un colorant direct diazoique cationique contenant une unite 2-imidazolium

Country Status (4)

Country Link
US (1) US20100031453A1 (fr)
EP (1) EP2032540A1 (fr)
FR (1) FR2901794A1 (fr)
WO (1) WO2008034650A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2940310A1 (fr) * 2008-12-18 2010-06-25 Oreal Composes dichromophoriques dicationiques de type hydrazone / diazoique, compositions tinctoriales les comprenant, procede de coloration de fibres keratiniques
EP2868702A1 (fr) 2013-10-29 2015-05-06 DyStar Colours Distribution GmbH Colorants dispersives, leur préparation et utilisation
CN105315711A (zh) * 2015-10-28 2016-02-10 江苏德旺化工工业有限公司 一种分散深黑染料组合物
US9388161B2 (en) 2013-11-18 2016-07-12 Forma Therapeutics, Inc. Tetrahydroquinoline compositions as BET bromodomain inhibitors
US10377769B2 (en) 2013-11-18 2019-08-13 Forma Therapeutics, Inc. Benzopiperazine compositions as BET bromodomain inhibitors

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107074737B (zh) 2014-11-04 2019-07-16 诺赛尔股份有限公司 2-甲氧基甲基-对苯二胺的叠缩合成
WO2016073276A1 (fr) 2014-11-04 2016-05-12 The Procter & Gamble Company Synthèse emboîtée de 2-méthoxyméthyl-p-phénylènediamine
WO2016073277A1 (fr) 2014-11-04 2016-05-12 The Procter & Gamble Company Procédé de préparation de 1,4-benzène diamines 2-substituées et sels de celles-ci
MX361963B (es) 2014-11-04 2018-12-19 Noxell Corp Colorantes azoicos directos y método para teñir el pelo usando estos colorantes.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3102879A (en) * 1958-09-30 1963-09-03 Basf Ag Production of cationic dyestuffs
US3173907A (en) * 1959-11-27 1965-03-16 American Cyanamid Co Quaternized n-alkylated arylazoimidazoles
GB2022099A (en) * 1978-05-26 1979-12-12 Hoechst Ag Process for spin-dyeing homopolymers or copolymers of acrylonitrile
FR2825703A1 (fr) * 2001-06-11 2002-12-13 Oreal Composition pour la teinture des fibres keratiniques comprenant un colorant diazoique dicationique particulier
WO2005058840A2 (fr) * 2003-12-19 2005-06-30 Ciba Specialty Chemicals Holding Inc. Procede de coloration a l'aide d'un compose diazote coiffe et d'un constituant de couplage

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3051697A (en) * 1958-10-06 1962-08-28 American Cyanamid Co Azomonazone n-oxides, production and deoxygenation
BE655513A (fr) * 1963-11-22
DE1544360A1 (de) * 1964-04-22 1969-07-10 Basf Ag Verfahren zur Herstellung von heterocyclischen Disazofarbstoffen
FR2586913B1 (fr) * 1985-09-10 1990-08-03 Oreal Procede pour former in situ une composition constituee de deux parties conditionnees separement et ensemble distributeur pour la mise en oeuvre de ce procede
DE3843892A1 (de) * 1988-12-24 1990-06-28 Wella Ag Oxidationshaarfaerbemittel mit einem gehalt an diaminopyrazolderivaten und neue diaminopyrazolderivate
DE4133957A1 (de) * 1991-10-14 1993-04-15 Wella Ag Haarfaerbemittel mit einem gehalt an aminopyrazolderivaten sowie neue pyrazolderivate
US5792221A (en) * 1992-06-19 1998-08-11 L'oreal Hydroxypropylated 2-nitro-p-phenylenediamines, and compositions for dyeing keratinous fibers which contain hydroxypropylated 2-nitro-p-phenylenediamines
DE4234887A1 (de) * 1992-10-16 1994-04-21 Wella Ag Oxidationshaarfärbemittel mit einem Gehalt an 4,5-Diaminopyrazolderivaten sowie neue 4,5-Diaminopyrazolderivate und Verfahren zu ihrer Herstellung
US5663366A (en) * 1992-10-16 1997-09-02 Wella Aktiengesellschat Process for the synthesis of 4,5-diaminopyrazole derivatives useful for dyeing hair
US5888252A (en) * 1993-11-30 1999-03-30 Ciba Specialty Chemicals Corporation Processes for dyeing keratin-containing fibres with cationicazo dyes
EP0714954B1 (fr) * 1994-11-03 2002-09-25 Ciba SC Holding AG Colorants cationiques glyoxalin azoiques
DE4440957A1 (de) * 1994-11-17 1996-05-23 Henkel Kgaa Oxidationsfärbemittel
FR2733749B1 (fr) * 1995-05-05 1997-06-13 Oreal Compositions pour la teinture des fibres keratiniques contenant des diamino pyrazoles, procede de teinture, nouveaux diamino pyrazoles et leur procede de preparation
DE19543988A1 (de) * 1995-11-25 1997-05-28 Wella Ag Oxidationshaarfärbemittel mit einem Gehalt an 3,4,5-Triaminopyrazolderivaten sowie neue 3,4,5-Triaminopyrazolderivate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3102879A (en) * 1958-09-30 1963-09-03 Basf Ag Production of cationic dyestuffs
US3173907A (en) * 1959-11-27 1965-03-16 American Cyanamid Co Quaternized n-alkylated arylazoimidazoles
GB2022099A (en) * 1978-05-26 1979-12-12 Hoechst Ag Process for spin-dyeing homopolymers or copolymers of acrylonitrile
FR2825703A1 (fr) * 2001-06-11 2002-12-13 Oreal Composition pour la teinture des fibres keratiniques comprenant un colorant diazoique dicationique particulier
WO2005058840A2 (fr) * 2003-12-19 2005-06-30 Ciba Specialty Chemicals Holding Inc. Procede de coloration a l'aide d'un compose diazote coiffe et d'un constituant de couplage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CHEMLIST 11 January 1996 (1996-01-11), XP002419056, retrieved from STN accession no. 190741 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2940310A1 (fr) * 2008-12-18 2010-06-25 Oreal Composes dichromophoriques dicationiques de type hydrazone / diazoique, compositions tinctoriales les comprenant, procede de coloration de fibres keratiniques
EP2868702A1 (fr) 2013-10-29 2015-05-06 DyStar Colours Distribution GmbH Colorants dispersives, leur préparation et utilisation
US9567464B2 (en) 2013-10-29 2017-02-14 Dystar Colours Distribution Gmbh Disperse dyes, their preparation and their use
US9388161B2 (en) 2013-11-18 2016-07-12 Forma Therapeutics, Inc. Tetrahydroquinoline compositions as BET bromodomain inhibitors
US10336722B2 (en) 2013-11-18 2019-07-02 Forma Therapeutics, Inc. Tetrahydroquinoline compositions as BET bromodomain inhibitors
US10377769B2 (en) 2013-11-18 2019-08-13 Forma Therapeutics, Inc. Benzopiperazine compositions as BET bromodomain inhibitors
US10611750B2 (en) 2013-11-18 2020-04-07 Forma Therapeutics, Inc. Tetrahydroquinoline compositions as bet bromodomain inhibitors
US10703764B2 (en) 2013-11-18 2020-07-07 Forma Therapeutics, Inc. Benzopiperazine compositions as BET bromodomain inhibitors
US11084831B1 (en) 2013-11-18 2021-08-10 Forma Therapeutics, Inc. Benzopiperazine compositions as BET bromodomain inhibitors
US11111229B2 (en) 2013-11-18 2021-09-07 Forma Therapeutics, Inc. Tetrahydroquinoline compositions as BET bromodomain inhibitors
CN105315711A (zh) * 2015-10-28 2016-02-10 江苏德旺化工工业有限公司 一种分散深黑染料组合物

Also Published As

Publication number Publication date
US20100031453A1 (en) 2010-02-11
EP2032540A1 (fr) 2009-03-11
FR2901794A1 (fr) 2007-12-07

Similar Documents

Publication Publication Date Title
KR100855928B1 (ko) 하나 이상의 2-피리디늄기 및 양이온성 또는 비-양이온성링커를 가지는 대칭 디아조 화합물, 이를 함유하는 조성물,착색 방법 및 장치
KR100911642B1 (ko) 하나 이상의 2-이미다졸륨 단위체 및 양이온성 또는비-양이온성 링커를 가지는 비대칭 디아조 화합물, 이를포함하는 조성물, 착색 방법, 및 장치
KR100851260B1 (ko) 2-이미다졸륨기 및 비-양이온성 링커를 함유한 대칭 디아조화합물, 이를 함유하는 조성물, 착색 방법 및 장치
US20060156490A1 (en) Symmetrical diazo compounds comprising 2-imidazolium groups and a cationic linker, compositions comprising them, method of coloring, and device
KR20060067912A (ko) 2-피리디늄기 및 양이온성 또는 비-양이온성 링커를함유하는 비대칭 디아조 화합물, 이를 함유하는 조성물,착색 방법 및 장치
MX2007007182A (es) Compuestos diazo disimetricos, composiciones que comprenden los mismos, metodo de coloracion y dispositivo que comprende tales composiciones.
WO2006063867A2 (fr) Composes diazo symetriques contenant des groupes 3-pyridinium et un lieur non cationique, compositions les renfermant, procede de coloration et dispositif
JP2006009017A (ja) 特定のカチオン性ジアゾ化合物、直接染料としてそれを含む組成物、ケラチン繊維の染色方法、およびそのためのデバイス
WO2008034650A1 (fr) Composition de coloration de fibres de keratine comprenant un colorant direct diazoique cationique contenant une unite 2-imidazolium
JP2009067772A (ja) ピラゾリノン単位を備えたアゾメチン化合物を含む着色組成物
US7247713B2 (en) Symmetrical diazo compounds containing 2-pyridinium groups and cationic or non-cationic linker, compositions comprising them, method of coloring, and device
EP2170260B1 (fr) Derives azo contenant une unite pyrazolinone pour colorer des fibres de keratine
US20090062517A2 (en) Dissymmetrical Diazo Compounds Containing Having at Least One 2-imidazolium Unit and a Cationic or Non-cationic Linker, Compositions Comprising Them, Method of Coloring, and Device
MXPA05013636A (es) Compuestos diazoicos simetricos con grupos 4-piridinio y brazo de union cationico o no, composiciones que los contienen, procedimiento de coloracion y dispositivo.
KR100878173B1 (ko) 하나 이상의 4-피리디늄 단위체 및 양이온성 또는비-양이온성 링커를 가지는 비대칭 디아조 화합물, 이를함유하는 조성물, 착색 방법 및 장치
US7288639B2 (en) Dyssymmetrical diazo compounds having at least one 4-pyridinium unit and a cationic or non-cationic linker, compositions comprising them, method of coloring, and device
US7396368B2 (en) Symmetrical diazo compounds comprising 4-pyridinium groups and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device
US7438728B2 (en) Dissymmetrical diazo compounds comprising 2-pyridinium group and a cationic or non-cationic linker, compositions comprising them, method for coloring, and device
EP3474814B1 (fr) Un composé de type azométhine portant un motif dérivé de quinoléine et son utilisation pour la teinture des fibres kératiniques
US7282069B2 (en) Cationic diazo compounds, compositions comprising them as direct dye, process for dyeing keratin fibers and device therefor
KR20070073937A (ko) 케라틴 섬유의 염색을 위한, 대칭 양이온성 테트라아조화합물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07857191

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2007857191

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

WWE Wipo information: entry into national phase

Ref document number: 12302658

Country of ref document: US