Abstract:
5-Nitroisatin is reacted with sodium hydroxide to produce an α-keto acid sodium salt that is reduced with borane-tetrahydrofuran complex and then hydrogenated to produce 1-(2,5-diaminophenyl)ethylene glycol, a novel compound useful as a primary intermediate in the production of oxidative hair dyes.

Description:
FIELD OF THE INVENTION 
     The invention relates to 1-(2,5-diaminophenyl)ethylene glycol (1), to a process for preparing same and to its use in compositions for dyeing human hair.                           
     BACKGROUND OF THE INVENTION 
     Compositions for the oxidative dyeing of hair comprise primary intermediates (such as p-phenylenediamine, p-toluenediamine, p-aminophenol, 4-amino-3-methylphenol) and couplers (such as resorcinol, 2-methylresorcinol, 3-aminophenol, 5-amino-2-methylphenol). A majority of shades have been produced with dyes based on p-phenylenediamine. However, as noted in U.S. Pat. Nos. 5,599,353 and 5,538,516, the use of p-phenylenediamine is being questioned for toxicological reasons, mainly due to its sensitization potential. 
     Because of the supposed toxicological issues attendant to its use, the art has been looking for substitutes for p-phenylenediamine. 
     EP 400,330 B1 (GB 2,239,265 A) describes the use of 2-(2-hydroxyethyl)-p-phenylenediamine as a replacement for p-phenylenediamine. 
     Pyrimidine derivatives, such as tetraaminopyrimidine, have been also suggested as alternatives to p-phenylenediamine (see U.S. Pat. No. Re. 30,199 [U.S. Pat. No. 4,003,699]). However, GB 2,239,265 A, points out that although the use of pyrimidine derivatives as developers has reduced toxicological problems, the pyrimidine derivatives are not completely satisfactory with respect to coloring performance. 
     U.S. Pat. No. 5,421,833 discloses hair dye compositions asserted to be without sensitizing potential. The dye compositions are disclosed to possess improved dyeing properties for all shades. The compositions comprise only 2-(2′-hydroxyethyl)amino-5-aminotoluene in combination with the usual coupling agents (with the exclusion of 1-methoxy-2,4-diaminobenzene and 1-ethoxy-2,4-diaminobenzene). 
     The object of the present invention was to develop a p-phenylenediamine alternative having less sensitization potential. This proved to be a difficult task. Since the structure-sensitization relationship is not known, it is difficult to predict whether a hair dye molecule will exhibit much lower potential for sensitization than p-phenylenediamine. Surprisingly and unexpectedly, we have found that 1-(2,5-diaminophenyl)ethylene glycol is a much weaker sensitizer than p-phenylenediamine. 
     SUMMARY OF THE INVENTION 
     The present invention provides the novel compound, 1-(2,5-diaminophenyl)ethylene glycol, a process for preparing same, its use as a primary intermediate in oxidative hair dyeing, and hair dye compositions containing same. 
     In contrast to p-phenylenediamine, 1-(2,5-diaminophenyl)ethylene glycol was surprisingly found to be a weak sensitizer. 
     Current technology generally requires p-phenylenediamine or p-toluenediamine for producing red and black shades (see U.S. Pat. No. 5,538,516). 
     The present invention enables one skilled in the art to formulate a natural black shade and dark red shade through the use of 1-(2,5-diaminophenyl)ethylene glycol without relying on p-phenylenediamine (see Table 2). 
     Advantageously, the shades obtained through use of 1-(2,5-diaminophenyl)ethylene glycol have good wash and light fastness. 
     The process for the preparation of the 1-(2,5-diaminophenyl)ethylene glycol is new and commercially feasible. The synthesis of the compound  1  requires three steps: (1) ring-opening of 5-nitroisatin with sodium hydroxide, (2) borane reduction of the keto acid, and (3) hydrogenation. 
     1-(2,5-Diaminophenyl)ethylene glycol has excellent solubility in water. Four grams of 1-(2,5-diaminophenyl)ethylene glycol sulfate salt completely dissolves in 100 ml of water at room temperature. The p-toluenediamine sulfate salt is partially soluble under the same conditions. Water solubility is important because hair dye formulations employed for hair coloring are in large part water. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The following examples are intended to illustrate the present invention and not to limit same in any respect. It should be noted that where percentage is employed, unless indicated to the contrary, it is percent by weight and is based on total weight. 
     1. The synthesis of 1-(2,5-diaminophenyl)ethylene glycol (compound 1): 
     The synthesis of compound 1 was carried out according to the following scheme.                           
     A solution of 5-nitroisatin, compound 2, (96.07 g, 500 mmole) with sodium hydroxide solution (200 mL, 5.5 M solution) in ethanol (200 mL) was stirred at room temperature for 1 hour. The resulting solid was collected and washed with acetone to give compound 3 (116.71 g, 100% yield): mp 281° C. decomposed;  1 H NMR (300 MHz, DMSO-d 6 ) δ 6.80 (d, 1H, J=9.3 Hz), 8.01 (dd, 1H, J=9.3, 2.7 Hz), 8.46 (d, 1H, J=2.7 Hz), 8.75 (bs, 2H). 
     Borane-THF (1.0M, 1.2 L) was added dropwise over a period of 2.5 hours to a stirred suspension of the α-keto acid sodium salt (3) (92.86 g, 400 mmole) in 400 mL tetrahydrofurane (THF) at 4° C. After the borane addition was complete, the reaction mixture was warmed to ambient temperature and stirred for 16 hours. The excess borane was quenched at 4° C. with methanol and the reaction mixture was evaporated under vacuum. The residue was dissolved in 400 mL water and acidified to pH 2-3 with concentrated hydrochloric acid. The resulting precipitate was collected and air-dried to afford compound 4 (78.15 g, 98.6% yield): mp 154-156° C.:  1 H NMR (300 MHz, DMSO-d 6 ) δ 3.44 (m, 2H), 4.65 (q, 1H, J=10, 4.8 Hz), 4.70 (t, 1H, J=6.0 Hz), 5.47 (d, 1H, J=4.2 Hz), 6.47 (s, 2H), 6.62 (d, 1H, J=9.0 Hz), 7.84 (dd, 1H, J=9.0, 2.7 Hz), 8.04 (d, 1H, J=2.7 Hz); MS m/z 198 (M + ). 
     A mixture of compound 4 (21.80 g, 110 mmole) and 10% Pd/C (2.2 g) in CH 3 OH/acetic acid (150/15 mL) was hydrogenated at 60 psi for 2.5 hours. The mixture was filtered over a layer of Celite and washed with methanol. The combined filtrate was neutralized with concentrated ammonium hydroxide. The resulting precipitate was filtered to give the compound 1 (15.11 g, 81.8% yield): mp 153-154° C.;  1 H NMR (300 MHz, DMSO-d 6 ) δ 3.40 (m, 2H), 4.12 (s, 2H), 4.17 (s, 2H), 4.49 (t, 1H, J=6 Hz), 4.60 (s, 1H), 5.05 (s, 1H), 6.24 (dd, 1H, J=8.1, 2.7 Hz), 6.35 (d, 1H, J=8.1 Hz), 6.44 (d, 1H, J=2.4 Hz); MS m/z 168 (M + ). 
     2. Compositions 
     Dye compositions containing 1-(2,5-diaminophenyl)ethylene glycol can also contain other primary intermediates and couplers. 
     It should be noted that for certain dark shades, including dark brown and black shades, it is desirable to include a meta diamine as one of the couplers. Suitable meta diamines include m-phenylenediamine, 2,4-diaminophenoxyethanol and 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine. 
     Suitable primary intermediates include: 
     p-Phenylenediamine derivatives such as: p-toluenediamine; p-phenylenediamine; 2-chloro-p-phenylenediamine; N-phenyl-p-phenylenediamine; N-2-methoxyethyl-p-phenylenediamine; N,N-bis(2-hydroxyethyl)-p-phenylenediamine; 2-hydroxymethyl-p-phenylenediamine; 2-hydroxyethyl-p-phenylenediamine; 4,4′-diaminodiphenylamine; 2,6-dimethyl-p-phenylenediamine; 2-isopropyl-p-phenylenediamine; N-(2-hydroxypropyl)-p-phenylenediamine; 2-propyl-p-phenylenediamine; 1,3-bis(N-hydroxyethyl)-N-(4-aminophenyl)amino-2-propanol and 2-methyl-4-dimethylaminoaniline; 
     p-Aminophenol derivatives such as: p-aminophenol; p-methylaminophenol; 3-methyl-p-aminophenol; 2-hydroxymethyl-p-aminophenol; 2-methyl-p-aminophenol; 2-(2′-hydroxyethylaminomethyl)-p-aminophenol; 2-methoxymethyl-p-aminophenol; 5-aminosalicylic acid and 1-(4-amino-2-hydroxyphenyl)-ethane-1,2-diol; 
     Ortho-developers such as: catechol; pyrogallol; o-aminophenol; 2,4-diaminophenol; 2,4,5-trihydroxytoluene; 1,2,4-trihydroxybenzene; 2,3-dihydroxynaphthalene; 5-methyl-o-aminophenol; 6-methyl-o-aminophenol and 2-amino-5-acetaminophenol and; 
     Heterocyclic derivatives such as: 2,4,5,6-tetra-aminopyrimidine; 4,5-diamino-1-methyl-pyrazole and 2-dimethylamino-5-aminopyridine; 
     Suitable couplers include: 
     Phenols, resorcinol and naphthol derivatives such as: 1,7-dihydroxynaphthalene; resorcinol; 4-chlororesorcinol; 1-naphthol; 2-methyl-1-naphthol; 1-acetoxy-2-methyl naphthalene; 1,5-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; hydroquinone; 2-methylresorcinol; 1-hydroxy-6-aminonaphthalene-3-sulfonic acid; thymol (2-isopropyl-5-methylphenol); 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene; 2-chlororesorcinol; 2,3-dihydroxy-1,4-naphthoquinone and 1-naphthol-4-sulfonic acid; 
     m-Phenylenediamines such as: m-phenylenediamine; 2,4-diaminophenoxyethanol; N,N-bis(2-hydroxyethyl)-m-phenylenediamine; 2,6-diaminotoluene; 2-N,N-bis(hydroxyethyl)-2,4-diaminophenetole; bis(2,4-diaminophenoxy)-1,3-propane; 1-hydroxyethyl-2,4-diaminobenzene; 2-amino-4-hydroxyethylaminoanisole; 1-aminoethoxy-2,4-diaminobenzene; 2,4-diaminophenoxyacetic acid; 4,6-bis(hydroxyethoxy)-m-phenylenediamine; 2,4-diamino-5-methylphenetole; 2,4-diamino-5-hydroxyethoxytoluene; 2,4-dimethoxy-1,3-diaminobenzene and 2,6-bis(hydroxyethylamino)-toluene; 
     m-Aminophenols such as: m-aminophenol; 2-hydroxy-4-carbamoylmethylamino toluene; m-carbamoylmethylaminophenol; 6-hydroxybenzomorpholine; 2-hydroxy-4-aminotoluene; 2-hydroxy-4-hydroxyethylaminotoluene; 4,6-dichloro-m-aminophenol; 2-methyl-m-aminophenol; 2-chloro-6-methyl-m-aminophenol; 2-hydroxyethoxy-5-aminophenol; 2-chloro-5-trifluoroethylaminophenol; 4-chloro-6-methyl-m-aminophenol; N-cyclopentyl-3-aminophenol; N-hydroxyethyl-4-methoxy-2-methyl-m-aminophenol and 5-amino-4-methoxy-2-methylphenol and 
     Heterocyclic derivatives such as: 1-phenyl-3-methyl-5-pyrazolone; 6-methoxy-8-aminoquinoline; 2,6-dihydroxy-4-methylpyridine; 5-hydroxy-1,4-benzodioxane; 3,4-methylenedioxyphenol; 4-hydroxyethylamino-1,2-methylenedioxybenzene; 2,6-dihydroxy-3,4-dimethylpyridine; 5-chloro-2,3-dihydroxypyridine; 3,5-diamino-2,6-dimethoxypyridine; 2-hydroxyethylamino-6-methoxy-3-aminopyridine; 3,4-methylenedioxyaniline; 2,6-bis(2-hydroxyethoxy)-3,5-diaminopyridine; 4-hydroxyindole; 3-amino-5-hydroxy-2,6-dimethoxypyridine; 5,6-dihydroxyindole; 7-hydroxyindole; 5-hydroxyindole; 2-bromo-4,5-methylenedioxyphenol; 6-hydroxyindole; 3-amino-2-methylamino-6-methoxypyridine; 2-amino-3-hydroxypyridine; 2,6-diaminopyridine; 5-(3,5-diamino-2-pyridyloxy)-1,3-dihydroxypentane; 3-(3,5-diamino-2-pyridyloxy)-2-hydroxypropanol and 4-hydroxy-2,5,6-triaminopyrimidine. 
     Preferred primary intermediates include: 
     p-Phenylenediamine derivatives such as: p-toluenediamine; p-phenylenediamine; N-2-methoxyethyl-p-phenylenediamine; N,N-bis(2-hydroxyethyl)-p-phenylenediamine; 2-hydroxyethyl-p-phenylenediamine; 
     p-Aminophenol derivatives such as: p-aminophenol; p-methylaminophenol; 3-methyl-p-aminophenol; 2-methoxymethyl-p-aminophenol and 1-(5-amino-2-hydrxyphenyl)-ethane-1,2-diol; 
     Ortho-developers such as: o-aminophenol; 1,2,4-trihydroxybenzene; 2-ethylamino-p-cresol; 5-methyl-2-aminophenol; 6-methyl-2-aminophenol and 2-amino-5-acetaminophenol and 
     Heterocyclic derivatives such as: 2,4,5,6-tetra-aminopyrimidine and 4,5-diamino-1-methylpyrazole. 
     Preferred couplers include: 
     Phenols, resorcinol and naphthol derivatives such as: 2-methyl-1-naphthol; 1-acetoxy-2-methylnaphthalene; 1,7-dihydroxynaphthalene; resorcinol; 4-chlororesorcinol; 1-naphthol; 1,5-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; hydroquinone; 2-methylresorcinol and thymol (2-isopropyl-5-methylphenol); 
     m-Phenylenediamines such as: m-phenylenediamine; 2,4-diaminophenoxyethanol; 1,3-bis(2,4-diaminophenoxy)propane; 2-amino-4-hydroxyethylamino anisole and 4,6-bis(hydroxyethoxy)-m-phenylenediamine; 
     m-Aminophenols such as: m-aminophenol; 6-hydroxybenzomorpholine; 2-hydroxy-4-aminotoluene; 2-hydroxy-4-hydroxyethylaminotoluene and 2-methyl-m-aminophenol and 
     Heterocyclic derivatives such as: 4,5-diamino-1-methyl-pyrazole; 2-dimethylamino-5-aminopyridine; 1-phenyl-3-methyl-5-pyrazolone; 3,4-methylenedioxyphenol; 3,4-methylenedioxyaniline; 4-hydroxyindole; 5,6-dihydroxyindole; 7-hydroxyindole; 5-hydroxyindole; 6-hydroxyindole; 2,6-diaminopyridine and 2-amino-3-hydroxypyridine. 
     Most preferred primary intermediates include: 
     p-Phenylenediamine derivatives such as: p-toluenediamine; p-phenylenediamine; N,N-bis(2-hydroxyethyl)-p-phenylenediamine and 2-hydroxyethyl-p-phenylenediamine; 
     p-Aminophenol derivatives such as: p-aminophenol; p-methylaminophenol; 3-methyl-p-aminophenol and 1-(5-amino-2-hydroxyphenyl)-ethane-1,2-diol; 
     Ortho-developers such as: o-aminophenol; 1,2,4-trihydroxybenzene; 2-ethylamino-p-cresol; 5-methyl-2-aminophenol; 6-methyl-2-aminophenol and 2-amino-5-acetaminophenol. 
     Most preferred couplers include: 
     Phenols, resorcinol and naphthol derivatives such as: 2-methyl-1-naphthol; 1-acetoxy-2-methylnaphthalene; resorcinol; 4-chlororesorcinol; 1-naphthol and 2-methylresorcinol; 
     m-Phenylenediamines such as: 2,4-diaminophenoxyethanol; 2-amino-4-hydroxyethylamino anisole and 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine; and 
     Heterocyclic derivatives such as: 4,5-diamino-1-methyl-pyrazole: 1-phenyl-3-methyl-5-pyrazolone; 2-amino-3-hydroxypyridine and 6-hydroxyindole. 
     Preferred combinations employing 1-(2,5-diaminophenyl) ethane-1,2-diol as a p-phenylenediamine replacement include combinations 1-24 set forth in Table 1 which follows: 
     Combination 1 of Table 1 is a mixture of 1-(2,5-diaminophenyl) ethane-1,2-diol; 2-[(4-aminophenyl)-(2-hydroxy-ethyl)-amino]-ethanol; 2-amino-phenol; benzene-1,3-diol; naphthalen-1-ol; 3-amino-phenol; and 4-amino-phenol. 
     In reading Table 1, reading down the column headed 2, the components of combination 2 are indicated by x&#39;es. 
     The composition of each of the remaining combinations is similarly determined. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 COMBINATIONS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Structure 
                 IUPAC Name 
                 Name 
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
                 7 
                 8 
                 9 
                 10 
                 11 
                 12 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 1-(2,5-Diamino- phenyl)-ethane- 1,2-diol 
                 1-(2,5- Diaminophenyl)- ethylene glycol 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-[(4-Amino- phenyl)-(2- hydroxy-ethyl)- amino]-ethanol 
                 N,N-Bis(2- hydroxyethyl)-p- phenylene- diamine 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Amino-phenol 
                 o-Aminophenol 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Benzene-1,3-diol 
                 Resorcinol 
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl- benzene-1,3-diol 
                 2-Methyl- resorcinol 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Naphthalen-1-ol 
                 1-Naphthol 
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl- naphthalen-1-ol 
                 2-Methyl-1- naphthol 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-(2,4-Diamino- phenoxy)- ethanol 
                 2,4-diamino- phenoxyethanol 
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 3-Amino-phenol 
                 m-Aminophenol 
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5-Amino-2- methyl-phenol 
                 2-Hydroxy-4- aminotoluene 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 1H-Indole-5,6- diol 
                 5,6-Dihydroxy- indole 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Amino-pyridin- 3-ol 
                 2-Amino-3- hydroxypyridine 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amino-phenol 
                 p-Aminophenol 
                 X 
                 X 
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amino-3- methyl-phenol 
                 3-Methyl-p- aminophenol 
                   
                   
                 X 
                 X 
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 1-(5-Amino-2- hydroxy-phenyl)- ethane-1,2-diol 
                 1-(5-Amino-2- hydroxy-phenyl)- ethane-1,2-diol 
                   
                   
                   
                   
                 X 
                 X 
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 Structure 
                 IUPAC Name 
                 Name 
                 13 
                 14 
                 15 
                 16 
                 17 
                 18 
                 19 
                 20 
                 21 
                 22 
                 23 
                 24 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 1-(2,5-Diamino- phenyl)-ethane- 1,2-diol 
                 1-(2,5- Diaminophenyl)- ethylene glycol 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-[(4-Amino- phenyl)-(2- hydroxy-ethyl)- amino]-ethanol 
                 N,N-Bis(2- hydroxyethyl)-p- phenylene- diamine 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Amino-phenol 
                 o-Aminophenol 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Benzene-1,3-diol 
                 Resorcinol 
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl- benzene-1,3-diol 
                 2-Methyl- resorcinol 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Naphthalen-1-ol 
                 1-Naphthol 
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl- naphthalen-1-ol 
                 2-Methyl-1- naphthol 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-(2,4-Diamino- phenoxy)- ethanol 
                 2,4-diamino- phenoxyethanol 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 3-Amino-phenol 
                 m-Aminophenol 
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5-Amino-2- methyl-phenol 
                 2-Hydroxy-4- aminotoluene 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 1H-Indole-5,6- diol 
                 5,6-Dihydroxy- indole 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Amino-pyridin- 3-ol 
                 2-Amino-3- hydroxypyridine 
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amino-phenol 
                 p-Aminophenol 
                 X 
                 X 
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amino-3- methyl-phenol 
                 3-Methyl-p- aminophenol 
                   
                   
                 X 
                 X 
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 1-(5-Amino-2- hydroxy-phenyl)- ethane-1,2-diol 
                 1-(5-Amino-2- hydroxy-phenyl)- ethane-1,2-diol 
                   
                   
                   
                   
                 X 
                 X 
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
             
          
         
       
     
     3. General dyeing procedure: 
     The test composition (according to Table 2 and Table 3) is mixed with 100 g of 20 volume hydrogen peroxide. The resulting mixture is applied on gray hair and permitted to remain in contact with the hair for 30 minutes. The dyed hair is then shampooed and rinsed with water and dried. 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Composition for Dyeing Hair Red 
               
             
          
           
               
                   
                 Example 1 
                 Example 2 
                 Example 3 
                 Example 4 
                 Example 5 
               
               
                 Ingredients 
                 WT % 
                 WT % 
                 WT % 
                 WT % 
                 WT % 
               
               
                   
               
             
          
           
               
                 Cocamidopropyl betaine 
                 17.00 
                 17.00 
                 17.00 
                 17.00 
                 17.00 
               
               
                 Ethanolamine 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
               
               
                 Oleic acid 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
               
               
                 Citric acid 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
               
               
                 Ammonium hydroxide 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
               
               
                 Behentrimonium chloride 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
               
               
                 Sodium sulfite 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
               
               
                 EDTA 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
               
               
                 Erythorbic acid 
                 0.40 
                 0.40 
                 0.40 
                 0.40 
                 0.40 
               
               
                 1-(2,5-Diaminophenyl)ethane-1,2-diol 
                 2.66 
                 2.66 
                 2.00 
                 0.50 
                 0.50 
               
               
                 4-Aminophenol 
                 0.92 
                   
                   
                 2.50 
                 2.50 
               
               
                 3-Methyl-p-aminophenol 
                   
                 1.20 
               
               
                 2-Methyl-p-aminophenol 
                   
                   
                 1.75 
               
               
                 2-Methyl-5-aminophenol 
                 1.54 
                   
                 1.60 
                 1.00 
                 1.00 
               
               
                 2-Methyl-5-hydroxethyl aminophenol 
                   
                 0.75 
               
               
                 2-Amino-5-methylphenol 
                   
                   
                 0.10 
               
               
                 1-Naphthol 
                   
                   
                   
                 1.50 
               
               
                 2-Methyl-1-naphthol 
                   
                   
                   
                   
                 1.50 
               
               
                 Water 
                 qs to 100 
                 qs to 100 
                 qs to 100 
                 qs to 100 
                 qs to 100 
               
               
                 Color obtained on gray hair: 
                 Dark Red 
                 Burgundy Red 
                 Bright Red 
                 Bright Red 
                 Bright Red 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Composition for Dyeing Hair Black to Brown 
               
             
          
           
               
                   
                 Example 6 
                 Example 7 
                 Example 8 
                 Example 9 
                 Example 10 
               
               
                 Ingredients 
                 WT % 
                 WT % 
                 WT % 
                 WT % 
                 WT % 
               
               
                   
               
             
          
           
               
                 Cocamidopropyl betaine 
                 17.00 
                 17.00 
                 17.00 
                 17.00 
                 17.00 
               
               
                 Ethanolamine 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
                 2.00 
               
               
                 Oleic acid 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
                 0.75 
               
               
                 Citric acid 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
               
               
                 Ammonium hydroxide 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
                 5.00 
               
               
                 Behentrimonium chloride 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
                 0.50 
               
               
                 Sodium sulfite 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
               
               
                 EDTA 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
                 0.10 
               
               
                 Erythorbic acid 
                 0.40 
                 0.40 
                 0.40 
                 0.40 
                 0.40 
               
               
                 1-(2,5-Diaminophenyl)ethane-1,2-diol 
                 3.00 
                 1.00 
                 2.00 
                 0.05 
                 0.05 
               
               
                 N,N-Bis(2-hydroxyethyl)-p-phenylenediamine 
                 1.00 
                 1.00 
                 .75 
                   
                 0.05 
               
               
                 1-(4-Aminophenyl)pyrrolidine 
                   
                 1.00 
               
               
                 4-Aminophenol 
                   
                   
                   
                 0.10 
                 0.05 
               
               
                 2-Aminophenol 
                   
                   
                   
                 0.10 
                 0.10 
               
               
                 Resorcinol 
                 2.00 
                 2.00 
               
               
                 2-Methylresorcinol 
                   
                   
                 1.00 
                 0.20 
                 0.20 
               
               
                 m-Aminophenol 
                 1.50 
                 0.80 
                 0.80 
                 0.05 
                 0.10 
               
               
                 2,4-Diaminophenoxyethanol hydrochloride 
                   
                 0.50 
               
               
                 4,6-Bis(2-hydroxyethoxy)-m-phenylenediamine 
                 2.00 
               
               
                 2-Amino-3-hydroxypyridine 
                   
                 0.50 
               
               
                 1-Naphthol 
                 1.00 
                   
                   
                 0.03 
                 0.02 
               
               
                 2-Methyl-1-naphthol 
                   
                   
                 0.25 
               
               
                 Water 
                 qs to 100 
                 qs to 100 
                 qs to 100 
                 qs to 100 
                 qs to 100 
               
               
                 Color obtained on gray hair: 
                 Black 
                 Dark Brown 
                 Medium Brown 
                 Golden Blonde 
                 Ash Blonde