Novel azo compounds, use in dyeing, compositions containing them and dyeing processes

Abstract

Azo compounds of the 2-(4-amino)phenyldiazinecarboximidamide type and 2-(4-amino)phenylhydrazinecarboximidamide type, a process for their synthesis, their use for dyeing keratin fibers, dye compositions containing them, and dyeing processes.

What is claimed is:  
     
         1 . An azo compound of formula (I) or the acid addition salt thereof:  
       
         
           
           
               
               
           
         
       
       in which: 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring.  
 
     
     
         2 . The compound of  claim 1  or salt thereof, wherein the C 1 -C 6  alkyl radicals are chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and isohexyl radicals.  
     
     
         3 . The compound of  claim 1  or salt thereof, wherein the C 1 -C 6  monohydroxyalkyl radical is chosen from hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl radicals.  
     
     
         4 . The compound of  claim 1  or salt thereof, wherein the C 2 -C 6  polyhydroxyalkyl radical is chosen from dihydroxyethyl, dihydroxypropyl, trihydroxypropyl, and dihydroxybutyl radicals.  
     
     
         5 . The compound of  claim 1  or salt thereof, wherein the cycloalkyl radical is chosen from cyclohexyl and cyclopentyl.  
     
     
         6 . The compound of  claim 1  or salt thereof, wherein the aromatic rings are chosen from phenyl rings; phenyl rings substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; benzyl, pyrimidine, pyridazine, and benzimidazole rings.  
     
     
         7 . The compound of  claim 1  or salt thereof, wherein said 4- to 8-membered heterocycle is chosen from imidazole, benzotriazole, benzimidazole, pyrrolidine, piperidine, and morpholine rings.  
     
     
         8 . The compound of  claim 1  or salt thereof, wherein the aromatic ring A is a 6-membered ring chosen from phenyl, pyrimidine and pyridine rings, or a 5-membered ring chosen from pyrrole and pyrazole rings.  
     
     
         9 . The compound of  claim 1 , wherein the compound or salt thereof is chosen from: 
 2-(4-amino)phenyldiazinecarboximidamide,    N,N-dimethyl-2-(4-amino)phenyldiazinecarboximidamide,    N,N-diethyl-2-(4-amino)phenyldiazinecarboximidamide,    N,N-diisopropyl-2-(4-amino)phenyldiazinecarboximidamide,    N,N-dibutyl-2-(4-amino)phenyldiazinecarboximidamide,    2-(5-amino)-2-pyridyldiazinecarboximidamide,    and the acid addition salts thereof.    
     
     
         10 . A method for dyeing keratin fibers comprising the step of contacting said fibers, for a time sufficient to achieve said dyeing, with a compound of formula (II) or the acid addition salt thereof:  
       
         
           
           
               
               
           
         
       
       in which: 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring.  
 
     
     
         11 . A method for making a compound of formula (I) or the acid addition salt thereof comprising the steps of: 
 (a) carrying out a reduction reaction in a solvent medium on a compound of formula (III) below                           in which 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring; for a time sufficient to give a compound of formula (II) or the acid addition salt thereof:  
                     
  in which:  
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical, or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring; and  
   (b) oxidizing the compound of formula (II) in a solvent for a time sufficient to give the compound of formula (I) or an acid addition salt thereof:                           in which: 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring.  
   
     
     
         12 . A method of dyeing keratin fibers comprising applying to said keratin fibers a compound of formula (I) or salt according to  claim 1  for a time sufficient to obtain said dyeing.  
     
     
         13 . The method of  claim 12 , wherein said keratin fibers are human keratin fibers.  
     
     
         14 . The method of  claim 13 , wherein said human keratin fibers are hair.  
     
     
         15 . The method of  claim 10 , wherein the compound of formula (II) or salt thereof is chosen from: 
 2-(4-amino)phenylhydrazinecarboximidamide,    N,N-dimethyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-diethyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-diisopropyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-dibutyl-2-(4-amino)phenylhydrazinecarboximidamide,    2-(5-amino)-2-pyridylhydrazinecarboximidamide,    and the acid addition salts thereof.    
     
     
         16 . The method of  claim 10 , wherein the compound of formula (II) or salt thereof is chosen from: 
 N,N-dimethyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-diethyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-diisopropyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-dibutyl-2-(4-amino)phenylhydrazinecarboximidamide,    2-(5-amino)-2-pyridylhydrazinecarboximidamide,    and the acid addition salts thereof.    
     
     
         17 . The compound of formula (II′) or an acid addition salt thereof:  
       
         
           
           
               
               
           
         
       
       in which 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring,  
 with the proviso that at least one of the radicals R 1 , R 2 , R 3  and R 4  is other than a hydrogen atom.  
 
     
     
         18 . The compound or salt as claimed in  claim 17 , wherein said compound or salt is chosen from: 
 N,N-dimethyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-diethyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-diisopropyl-2-(4-amino)phenylhydrazinecarboximidamide,    N,N-dibutyl-2-(4-amino)phenylhydrazinecarboximidamide,    2-(5-amino)-2-pyridylhydrazinecarboximidamide,    and the acid addition salts thereof.    
     
     
         19 . A composition for dyeing keratin fibers, wherein said composition comprises, in a medium which is suitable for dyeing, at least one compound chosen from compounds of formula (I) and salts thereof:  
       
         
           
           
               
               
           
         
       
       in which: 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring and compounds of formula (II) and salts thereof:  
                     
  in which: 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring.  
 
 
     
     
         20 . The composition of  claim 19  wherein said keratin fibers are human keratin fibers.  
     
     
         21 . The composition of  claim 21  wherein said human keratin fibers are hair.  
     
     
         22 . The composition of  claim 19 , wherein said at least one compound represents from 0.0005 to 12% by weight relative to the total weight of the dye composition.  
     
     
         23 . The composition of  claim 22 , wherein said at least one compound represents from 0.005 to 6% by weight relative to the total weight of the dye composition.  
     
     
         24 . The composition of  claim 19 , wherein said medium suitable for dyeing comprises water or a mixture of water and at least one organic solvent chosen from C 1 -C 4  lower alkanols, glycerol, glycols, glycol ethers and aromatic alcohols.  
     
     
         25 . The composition of  claim 24  wherein said at least one organic solvent is present in proportions ranging from 1 to 40% by weight approximately relative to the total weight of the dye composition.  
     
     
         26 . The composition of  claim 25  wherein said at least one organic solvent is present in proportions ranging from 5 to 30%.  
     
     
         27 . The composition of  claim 19 , wherein said composition has a pH ranging from 3 to 12.  
     
     
         28 . The composition of  claim 27 , wherein said composition has a pH ranging from 5to 11.  
     
     
         29 . The composition of  claim 19 , wherein said composition contains an oxidizing agent.  
     
     
         30 . The composition of  claim 29 , wherein said oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, and enzymes.  
     
     
         31 . The composition of  claim 30 , wherein said persalts are chosen from perborates and persulfates.  
     
     
         32 . The composition of  claim 19 , wherein said composition contains at least one oxidation base and/or at least one coupler.  
     
     
         33 . The composition of  claim 32 , wherein said at least one oxidation base represents from 0.0005 to 12% by weight relative to the total weight of the dye composition.  
     
     
         34 . The composition of  claim 32 , wherein said at least one coupler represents from 0.0001 to 10% by weight relative to the total weight of the dye composition.  
     
     
         35 . The composition of  claim 33 , wherein said at least one oxidation base represents from 0.005 to 8% by weight relative to the total weight of the dye composition.  
     
     
         36 . The composition of  claim 34 , wherein said at least one coupler represents from 0.005 to 8% by weight relative to the total weight of the dye composition.  
     
     
         37 . The composition of  claim 19 , further comprising at least one adjuvant chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants, anionic, cationic, nonionic, amphoteric and zwitterionic polymers, inorganic and organic thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, conditioners, film-forming agents, ceramides, preserving agents and opacifiers.  
     
     
         38 . The composition of  claim 37  wherein said conditioners are chosen from modified and unmodified, volatile and non-volatile silicones.  
     
     
         39 . The composition of  claim 19 , wherein the said acid addition salts are chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates.  
     
     
         40 . The composition of  claim 19 , wherein the composition optionally contains one or more direct dyes chosen from anthraquinones, nitro derivatives of benzene, and azo dyes other than those chosen from formula (I) and (II).  
     
     
         41 . The composition of  claim 19 , which is provided in the form of a liquid, a cream, a gel or any other form suitable for dyeing keratin fibers.  
     
     
         42 . A method for dyeing keratin fibers, comprising the step of applying at least one dye composition of  claim 19  to the fibers for a period of time which is sufficient to develop the desired colouring.  
     
     
         43 . The method of  claim 42 , wherein said keratin fibers are human keratin fibers.  
     
     
         44 . The method of  claim 43 , wherein said human keratin fibers are hair.  
     
     
         45 . The method of  claim 42 , wherein said period of time ranges from 3 to 60 minutes.  
     
     
         46 . The method of  claim 45 , wherein said period of time ranges from 5 to 40 minutes.  
     
     
         47 . The method of  claim 42 , further comprising, prior to said applying step, the preliminary step of separately storing: 
 a composition (A) comprising, in a medium which is suitable for dyeing, at least one compound of formula (II) and    a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent, and    the step of then mixing said separately stored components together at the time of use and prior to said applying step.    
     
     
         48 . A multi-compartment dyeing device or kit for dyeing keratin fibers, comprising at least two compartments, wherein 
 a first compartment contains composition (A) comprising, in a medium which is suitable for dyeing, at least one compound of formula (II) or the acid addition salt thereof:                           in which: 
 R 1  and R 2 , independently of each other, represent a hydrogen atom; a C 1 -C 6  alkyl radical; a 5- or 6-membered cycloalkyl radical; a 5- or 6-membered aromatic ring; a 5- or 6-membered aromatic ring substituted with a C 1 -C 6  alkyl radical, a halogen atom, an amino radical, a hydroxyl radical, or a C 1 -C 6  alkoxy radical; or R 1  and R 2  form, together with the nitrogen atom to which they are attached, a 4- to 8-membered heterocycle, said heterocycle containing one or more hetero atoms chosen from sulfur, nitrogen and oxygen;  
 R 3  and R 4 , independently of each other, represent a hydrogen atom, a C 1 -C 6  alkyl radical, a C 1 -C 6  monohydroxyalkyl radical or a C 2 -C 6  polyhydroxyalkyl radical; and  
 A is a 5- to 6-membered aromatic ring which can be interrupted by one or more hetero atoms chosen from sulfur, nitrogen and oxygen, or fused to another 5- to 6-membered aromatic ring, and  
 a second compartment contains composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent.