Abstract:
Couplers for hair coloring compositions for oxidative dyeing of hair are compounds of the formula (1):                            
     wherein R is selected from the group consisting of C 1  to C 2  alkyl and hydroxyethyl; R 1  is selected from the group consisting of a hydrogen, hydroxy, nitro, halogen, C 1  to C 5  alkyl or haloalkyl, C 1  to C 5  alkoxy or cycloalkoxy, C 1  to C 5  hydroxyalkyl and C 1  to C 5  hydroxyalkoxy; Ar is an aromatic group, preferably an aromatic group selected from the group consisting of a furyl, thienyl, pyridyl, phenyl, 2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl or benzo[1,3]dioxol-4 or -5-yl group; and y=1 to 3.

Description:
RELATED APPLICATION 
     This application is a continuation-in-part of application Ser. No. 09/495,582, filed Feb. 1, 2000, now U.S. Pat. No. 6,200,353, issued Mar. 13, 2001. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to novel couplers for use in hair coloring compositions comprising one or more oxidative hair coloring agents in combination with one or more oxidizing agents. The invention also relates to hair coloring compositions of these novel couplers and to coloring or dyeing of hair using compositions containing these couplers. 
     BACKGROUND OF THE INVENTION 
     Coloration of hair is a procedure practiced from antiquity employing a variety of means. In modern times, the most extensively used method employed to color hair is to color hair by an oxidative dyeing process employing hair coloring systems utilizing one or more oxidative hair coloring agents in combination with one or more oxidizing agents. 
     Most commonly a peroxy oxidizing agent is used in combination with one or more oxidative hair coloring agents, generally small molecules capable of diffusing into hair and comprising one or more primary intermediates and one or more couplers. In this procedure, a peroxide material, such as hydrogen peroxide, is employed to activate the small molecules of primary intermediates so that they react with couplers to form larger sized compounds in the hair shaft to color the hair in a variety of shades and colors. 
     A wide variety of primary intermediates and couplers have been employed in such oxidative hair coloring systems and compositions. Among the primary intermediates employed there may be mentioned p-phenylenediamine, p-toluenediamine, p-aminophenol, 4-amino-3-methylphenol, and as couplers there may be mentioned resorcinol, 2-methylresorcinol, 3-aminophenol, and 5-amino-2-methylphenol. A majority of the shades have been produced with dyes based on p-phenylenediamine. 
     For providing an orange coloration to hair 2-methyl-5-aminophenol has been extensively used in combination with p-aminophenol as a primary intermediate. However, the resulting orange color on hair undergoes significant changes on exposure to light or shampooing. U.S. Pat. No. 4,065,255 and EP patent publications EP 634165 A1 and EP 667143 A1 suggest the use of 2-methyl-5-N-hydroxyethylaminophenol, 2-methyl-5-alkylaminophenol and 2-methyl-5-aminophenol as couplers. Therefore, there is a need for new orange couplers for use in oxidative hair dyeing compositions and systems. 
     BRIEF SUMMARY OF THE INVENTION 
     This invention provides novel orange couplers of the formula (1):                           
     wherein R is selected from C 1  to C 2  alkyl and hydroxyethyl; R 1  is hydrogen, hydroxy, nitro, halogen, C 1  to C 5  alkyl or haloalkyl, C 1  to C 5  alkoxy or cyclic alkoxy, C 1  to C 5  hydroxyalkyl and C 1  to C 5  hydroxyalkoxy; Ar is an aromatic group, preferably an aromatic group selected from a furyl, thienyl, pyridyl, phenyl, 2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl or benzo[1,3]dioxol-4 or -5-yl group; and y=1 to 3. The halogen may be fluorine, chlorine, bromine or iodine, preferable fluorine or chlorine. These novel couplers are used to provide coloration to hair in which there is good dye uptake by the hair and provides shades or colors which are stable over a relatively long period of time. The novel couplers provide for dyeing of hair that provides color or shades that possess good wash fastness and do not undergo the significant changes on exposure to light or shampooing as experienced with 2-methyl-5-aminophenol. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Preferred coupler compounds of this invention are those of formula (1)                           
     wherein R is a methyl group, R 1  is a hydrogen, hydroxy, fluoro, chloro, trifluoromethyl, methyl or methoxy group; Ar is a pyridyl, furyl or thienyl group; and y=1 to 3. 
     Especially preferred couplers of this invention are the following compounds: 
     Compound 1: 2-methyl-5-[(1H-pyrrol-2-yl-methyl)-amino]phenol, 
     Compound 2: 2-methyl-5-(furan-2-yl-methylamino)phenol, and 
     Compound 3: 2-methyl-5-(thiophen-2-yl-methylamino)phenol. 
     The novel coupler compounds of formula (1) of this invention are readily prepared by a reductive amination reaction of an aminophenol of formula (2) with an appropriate aromatic carboxaldehyde of formula (3) in the presence of a suitable reducing agent, such as sodium triacetoxyborohydride or sodium borohydride, according to the following reaction sequence: 
     wherein R, R 1  and Ar are as defined hereinbefore and R is preferably a methyl group.                           
     As a synthesis example an aromatic carboxyaldehyde (0.03 mmole) is treated with an excess of an aminophenol of formula (2) (44.3 mg, 1.2 equiv. %; where R is methyl) in 1% AcOH-DCE (dichloroethane) (4 mL). The mixture is agitated in a reaction vessel for about 1 hour at room temperature and then sodium triacetoxyborohydride (127 mg, 0.6 mmole) is added. The mixture is agitated for about 18 hours and then Argonaut PS-MB aldehyde (100 mg, 1.26 mmole/g loading) is added. The mixture is agitated for about 1 hour, filtered and rinsed with anhydrous DCE (2 mL). To the filtrate is added water (2 mL), shaken and the water removed by pipette. The organic layer is filtered through a Chem Elute™ column (Varian, 3 mL sample capacity) and washed with DCE (2×2 mL). The filtrate is evaporated in vacuum to yield the target compound of Formula (1). The resulting product is analyzed by HPLC and identified by MS., and some products characterized by  1 H NMR. 
     Compounds 1, 2, and 3 were prepared in the following Synthesis Examples 1 to 3 according to the aforedescribed reaction sequence. 
    
    
     SYNTHESIS EXAMPLE 1 
     Preparation of Compound 1: 
     To a stirred solution of 5-amino-2-methylphenol (9.84 g, 80 mmole) in methanol (100 mL) at 4° C. was added pyrrole-2-carboxaldehyde (11.41 g, 120 mmole) and sodium acetate (13.13 g, 160 mmole). The reaction mixture was stirred for 15 minutes and sodium borohydride (3.78 g, 100 mmole) was added portionwise over 1 hour at 4° C. After the addition was complete, the reaction was allowed to stir for an additional 3 hours. The reaction mixture was poured onto crushed ice slurry (200 g) and the resulting precipitate was collected and washed with cold water three times and air-dried to afford 2-methyl-5-[(1H-pyrrol-2-yl-methyl)amino]phenol (6.62 g, 41% yield): mp 115.4-116.8° C.;  1 HNMR (400 MHz, DMSO-d 6 ) δ 1.94 (s, 3H), 4.03 (d, 2H, J=5.6 Hz), 5.37 (t, 1H, J=5.6 Hz), 5.90 (m, 2H), 6.01 (dd, 1H, J=2.2, 8.0 Hz), 6.12 (d, 1H, J=2.1 Hz), 6.61 (m, 1H), 6.70 (d, 1H, J=8.1 Hz), 8.77 (s, 1H), 10.64 (s, 1H); MS m/z 202 (M + ). 
     SYNTHESIS EXAMPLE 2 
     Preparation of Compound 2: 
     To a stirred solution of 5-amino-2-methylphenol (12.30 g, 100 mmole) in methanol (100 mL) at 4° C. was added 2-furaldehyde (14.41 g, 150 mmole) and sodium acetate (16.41 g, 200 mmole). The reaction mixture was stirred for 15 minutes and sodium borohydride (4.73 g, 125 mmole) was added portionwise over 1 hour at 4° C. After the addition was complete, the reaction was allowed to stir for an additional 1.5 hours. The reaction mixture was poured onto crushed ice slurry (200 g) and the resulting precipitate was collected, washed with cold water three times and air-dried to afford 2-methyl-5-(furan-2-yl-methylamino)phenol (16.86 g, 83% yield): mp 126.8-128.5° C.;  1 HNMR (400 MHz, DMSO-d 6 ) δ 1.94 (s, 3H), 4.12 (d, 2H, J=6.1 Hz), 5.71 (t, 1H, J=6.1 Hz), 6.00 (dd, 1H, J=2.3, 8.0 Hz), 6.11 (d, 1H, J=2.2 Hz), 6.22 (d, 1H, J=3.0 Hz), 6.36 (m, 1H), 6.70 (d, 1H, J=8.1 Hz), 7.54 (t, 1H, J=0.8 Hz), 8.79 (s, 1H); MS m/z 203 (M + ). 
     SYNTHESIS EXAMPLE 3 
     Preparation of Compound 3: 
     To a solution of 5-amino-2-methylphenol (12.30 g, 100 mmole) in methanol (100 mL) at 4° C. was added 2-thiophenecarboxaldehyde (16.82 g, 150 mmole) and sodium acetate (16.41 g, 200 mmole). The reaction mixture was stirred for 15 minutes and sodium borohydride (4.73 g, 125 mmole) was added portionwise over 1 hour at 4° C. After the addition was complete, the reaction was allowed to stir for an additional 1.5 hours. The reaction mixture was poured onto crushed ice slurry (200 g) and the resulting precipitate was collected, washed with cold water three times and air-dried to afford 2-methyl-5-(thiophen-2-yl-methylamino)phenol (7.12 g, 32% yield): mp 130.8-132.6° C.;  1 HNMR (400 MHz, DMSO-d 6 ) δ 1.94 (s, 3H), 4.34 (d, 2H, J=6.0 Hz), 5.91 (t, 1H, J=6.1 Hz), 6.00 (dd, 1H, J=2.3, 8.0 Hz), 6.11 (d, 1H, J=2.2 Hz), 6.70 (d, 1H, J=8.1 Hz), 6.95 (dd, 1H, J=3.5, 5.0 Hz), 7.00 (dd, 1H, J=0.8, 3.4 Hz), 7.34 (dd, 1H, J=1.0, 5.0 Hz), 8.79 (s, 1H); MS m/z 219 (M + ). 
     SYNTHESIS EXAMPLES 4-37 
     Employing the required aromatic carboxaldeyde in the forgoing described synthesis procedure the following coupler compounds of this invention were prepared. Their structure and purity (determined by HPLC) are set forth in Table 1 hereinafter. 
     2-Methyl-5-[(pyridin-3-ylmethyl)-amino]-phenol 
     3-[(3-Hydroxy-4-methyl-phenylamino)-methyl]-benzonitrile 
     5-(2-Fluoro-benzylamino)-2-methyl-phenol 
     5-(3-Fluoro-benzylamino)-2-methyl-phenol 
     5-(2,3-Difluoro-benzylamino)-2-methyl-phenol 
     5-(2,4-Difluoro-benzylamino)-2-methyl-phenol 
     5-(2-Methoxy-benzylamino)-2-methyl-phenol 
     5-(2-Hydroxy-3-methyoxy-benzylamino)-2-methyl-phenol 
     2-Methyl-5-(3,4,5-trimethoxy-benzylamino)-phenol 
     5-(2-Hydroxy-benzylamino)-2-methyl-phenol 
     2-Methyl-5-(2,3,4-trimethoxy-benzylamino)-phenol 
     5-(2,3-Dimethoxy-benzylamino)-2-methyl-phenol 
     5-(2,5-Dimethoxy-benzylamino)-2-methyl-phenol 
     5-(2-Chloro-benzylamino)-2-methyl-phenol 
     5-(3-Chloro-benzylamino)-2-methyl-phenol 
     5-(3-Methoxy-benzylamino)-2-methyl-phenol 
     5-(2-Hydroxy-5-methoxy-benzylamino)-2-methyl-phenol 
     5-[(2,3-Dihydro-benzo[1,4]dioxin-6-ylmethyl)-amino]-2-methyl-phenol 
     5-(3-Hydroxy-4-methyl-benzylamino)-2-methyl-phenol 
     2-Methyl-5-(4-trifluoromethyl-benzylamino)-phenol 
     5-(4-Methoxy-3-methyl-benzylamino)-2-methyl-phenol 
     5-(3,5-Dimethyl-4-hydroxy-benzylamino)-2-methyl-phenol 
     5-(3,4-Difluoro-benzylamino)-2-methyl-phenol 
     5-(4-Methoxy-2,5-dimethyl-benzylamino)-2-methyl-phenol 
     5-(2,4-Dimethoxy-3-methyl-benzylamino)-2-methyl-phenol 
     2-Methyl-5-(2,4,5-trimethoxy-benzylamino)-phenol 
     5-(4-Methoxy-2,3-dimethyl-benzylamino)-2-methyl-phenol 
     5-Benzylamino-2-methyl-phenol 
     5-(4-Fluoro-benzylamino)-2-methyl-phenol 
     5-(4-Methoxy-benzylamino)-2-methyl-phenol 
     2-Methyl-5-[(5-methyl-thiophen-2-ylmethyl)-amino]-phenol 
     5-[(Benzo[1,3]dioxol-5-ylmethyl)-amino]-2-methyl-phenol 
     2-Methyl-5-(4-nitro-benzylamino)-phenol 
     5[(5-Bromo-furan-2-ylmethyl)amino]-2-methyl-phenol 
     Hair coloring compositions of this invention can contain the novel couplers of this invention as the sole coupler or can also contain other couplers in combination with primary intermediates. 
     Compound 1 couples with p-aminophenol and p-phenylenediamine to color piedmont hair bright orange and red-violet, respectively. Compound 2&#39;s dye uptake is not as strong as that of Compound 1 and provides color of less brightness than Compound 1. Compound 3 provides an even duller color to piedmont hair. 
     For hair coloring compositions of this invention, there may be used one or more suitable primary intermediates in combination with the novel couplers of this invention. Suitable primary intermediates include, for example, 
     p-phenylenediamine derivatives such as: 2-methyl-p-phenylenediamine, p-phenylene-diamine, 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-(1-hydroxyethyl)-p-phenylenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine, 4,4′-diamino-diphenylamine, 2,6-dimethyl-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(2-hydroxypropyl)-p-phenylenediamine, 2-propyl-p-phenylenediamine, 1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol, 2-methyl-4-dimethylamino-aniline, 2-methoxy-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 1-(2,5-diaminophenyl)-ethane-1,2-diol, 2-thien-2-yl-benzene-1,4-diamine, 1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-diethylbenzene, 2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-yl-benzene-1,4-diamine, 1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1,4-diamine, 2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol, N-[2-(2,5-diaminophenoxy)ethyl]acetamide, N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine, N,N-diisopropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol, 2-[(4-amino-3-methylphenyl)-(2-hydroxy-ethyl)amino]-ethanol; N-(2-methoxyethyl)benzene-1,4-diamine, 3-[(4-aminophenyl)amino]propan-1-ol, 3-[(4-aminophenyl)amino]propane-1,2-diol, N-{4-[(4-aminophenyl)amino]butyl}-benzene-1,4-diamine, and 2-[2-(2-{2-[(2,5-diaminophenyl)oxy]ethoxy}ethoxy)-ethoxy]benzene-1,4-diamine; 
     p-aminophenol derivatives such as: p-aminophenol, p-methylaminophenol, 3-methyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2methyl-4-aminophenol, 2-(2′-hydroxyethylaminomethyl)-4-aminophenol, 2-methoxy-methyl-4-aminophenol, 5-aminosalicylic acid, 1-(5-amino-2-hydroxyphenyl)-ethane-1,2-diol, 2-(2-hydroxyethyl)-4-aminophenol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-3-fluorophenol, 4-amino-2-(aminomethyl)phenol, and 4-amino-2-fluorophenol; 
     o-aminophenol derivatives such as: o-aminophenol, 2,4-diaminophenol, 5-methyl-2-aminophenol, 6-methyl-2-aminophenol, 2-amino-5-acetaminophenol and 4-methyl-2-aminophenol; and 
     heterocyclic derivatives such as: 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-1-methylpyrazole, 2-dimethylamino-5-aminopyridine, 1-(2-hydroxyethyl)-4,5-diaminopyrazole, 4-hydroxy-2,5,6-triaminopyrimidine, 2-(2-hydroxyethylamino)-6-methoxy-3-aminopyridine, 3-amino-2-methylamino-6-methoxypyridine, pyridine-2,5-diamine, 1-isopropyl-1H-pyrazole-4,5-diamine, 1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and 1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine. 
     The primary intermediates can be employed in the form of a free base or in the form of an acid additive salt thereof, such as, for example, as a hydrochloride, a hydrobromide, a sulfate or the like. 
     Suitable couplers include, for example, 
     phenols, resorcinol and naphthol derivatives such as: 1,7-dihydroxynaphthalene, resorcinol, 4-chlororesorcinol, 1-naphthol, 2-methyl-1-naphthol, 1-acetoxy-2-methylnaphthalene, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, hydroquinone, 2-methyl-resorcinol, 1-hydroxy-6-aminonaphthalene-3-sulfonic acid, 2-isopropyl-5-methyl-phenol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2-chlororesorcinol, 2,3-dihydroxy-1,4-naphthoquinone, 1-naphthol-4-sulfonic acid, 1,2,3-trihydroxy-benzene, naphthalene-2,3-diol, 4,5-dichloro-2-methylbenzene-1,3-diol and 4,6-dichlorobenzene-1,3-diol, and 3,4-diaminobenzoic acid; 
     m-phenylenediamines such as: m-phenylenediamine, 2,4-diaminophenol, 2,4-diamino-phenoxyethanol, N,N-bis(2-hydroxyethyl)-m-phenylenediamine, 2,6-diaminotoluene, 2-N,N-bis(hydroxyethyl)-2,4-diaminophenetole, 1,3-bis(2,4-diaminophenoxy)-propane, 1-hydroxyethyl-2,4-diaminobenzene, 2-amino-4-(2-hydroxyethylamino)-anisole, 4-(2-aminoethoxy)-1,3-diaminobenzene, 2,4-diaminophenoxyacetic acid, 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine, 2,4-diamino-5-methylphenetole, 2,4-diamino-5-hydroxyethoxy-toluene, 4,6-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)-toluene, 3-(2,4-diaminophenoxy)-1-propanol, N-[3-(dimethyl-amino)phenyl]urea, 4-methoxy-6-methylbenzene-1,3-diamine, 4-fluoro-6-methylbenzene-1,3-diamine, 2-({3-[2-hydroxyethyl)amino]-4,6-dimethoxy-phenyl}amino)-ethanol, 3-(2,4-diaminophenoxy)propane-1,2-diol, 2-[2-amino-4-(methylamino)-phenoxy)ethanol, 2-[(5-amino-2-ethoxyphenyl)-(2-hydroxy-ethyl)amino]ethanol, 2-[(3-aminophenyl)amino]ethanol, N-(2-aminoethyl)benzene-1,3-diamine, 4-{[(2,4-diaminophenyl)oxy]methoxy}benzene-1,3-diamine, and 2,4-dimethoxybenzene-1,3-diamine; 
     m-aminophenols such as: m-aminophenol, 5-amino-2-ethylphenol, 5-amino-2-methoxyphenyl, and 5-[(3-hydroxypropyl)amino]-2-methylphenol 2-hydroxy-4-(carbamoyl-methylamino)toluene, m-carbamoylmethylaminophenol, 2-hydroxy-4-aminotoluene, 2-hydroxy-4-(2-hydroxyethylamino)toluene, 4,6-dichloro-m-amino-phenol, 2-methyl-m-aminophenol, 2-chloro-6-methyl-m-aminophenol, 2-(2-hydroxyethoxy)-5-aminophenol, 2-chloro-5-trifluoroethylaminophenol, 4-chloro-6-methyl-m-aminophenol, N-cyclopentyl-3-aminophenol, N-hydroxyethyl-4-methoxy-6-methyl-m-aminophenol, 5-amino-4-methoxy-2-methylphenol, 3-(dimethyl-amino)-phenol, 3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol, 3-[(3-hydroxy-2-methylphenyl)amino]propane-1,2-diol, and 3-[(2-hydroxyethyl)amino]-2-methylphenol; and 
     heterocyclic derivatives such as: 1-phenyl-3-methyl-5-pyrazolone, 6-hydroxybenzomorpholine, 6-methoxy-8-aminoquinoline, 2,6-dihydroxy-4-methylpyridine, 5-hydroxy-1,4-benzodioxane, 3,4-methylenedioxyphenol, 4-(2-hydroxyethylamino)-1,2-methylene-dioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 5-chloro-2,3-dihydroxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 3,4-methylenedioxyaniline, 2,6-bis(2-hydroxy-ethoxy)-3,5-diaminopyridine, 4-hydroxyindole, 3-amino-5-hydroxy-2,6-dimethoxy-pyridine, 5,6-dihydroxyindole, 7-hydroxyindole, 5-hydroxyindole, 2-bromo-4,5-methylenedioxyphenol, 6-hydroxyindole, 2-amino-3-hydroxypyridine, 2,6-diamino-pyridine, 5-(3,5-diamino-2-pyridyloxy)-1,3-dihydroxypentane, 3-(3,5-diamino-2-pyridyloxy)-2-hydroxypropanol, isatin, indole-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine, 6-methoxypyridine-2,3-diamine, and 3,4-dihydro-2H-1,4-benzoxazin-6-amine. 
     Preferred primary intermediates include: 
     p-phenylenediamine derivatives such as: 2-methyl-p-phenylenediamine, p-phenylenediamine, N-(2-methoxyethyl)-p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(1-hydroxyethyl)-p-phenylenediamine 2-(2-hydroxyethyl)-p-phenylenediamine, and 2-(1,2-dihydroxyethyl)-p-phenylenediamine; 
     p-aminophenol derivatives such as: p-aminophenol, p-methylaminophenol, 3-methyl-4-aminophenol, 2-methoxymethyl-4-aminophenol, 1-(5-amino-2-hydroxyphenyl)-ethane-1,2-diol; 
     o-aminophenol derivatives such as: o-aminophenol, 5-methyl-2-aminophenol, 6-methyl-2-aminophenol and 2-amino-5-acetaminophenol, and 4-methyl-2-aminophenol; and 
     heterocyclic derivatives such as: 2,4,5,6-tetraaminopyrimidine 4,5-diamino-1-methylpyrazole, 1-(2-hydroxyethyl)-4,5-diaminopyrazole, and 2-dimethylamino-5-aminopyridine. 
     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 2-isopropyl-5-methylphenol; 
     m-phenylenediamines such as: m-phenylenediamine, 2,4-diamino-phenoxyethanol, 1,3-bis(2,4-diaminophenoxy)propane, 2-amino-4-(2-hydroxyethylamino)anisole and 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine, and 3-(2,4-diaminophenoxy)-1-propanol; 
     m-aminophenols such as: m-aminophenol, 6-hydroxybenzomorpholine, 2-hydroxy-4-aminotoluene, 2-hydroxy-4-(2-hydroxyethylamino)toluene and 2-methyl-m-aminophenol; and 
     heterocyclic derivatives such as: 1-phenyl-3-methyl-5-pyrazolone, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 4-hydroxyindole, 5,6-dihydroxyindole, 7-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, isatin, 2,6-diaminopyridine and 2-amino-3-hydroxypyridine. 
     Most preferred primary intermediates include: 
     p-phenylenediamine derivatives such as: 2-methyl-p-phenylenediamine, p-phenylenediamine, N,N-bis(2-hydroxyethyl)-p-phenylenediamine and 2-(1-hydroxyethyl)-p-phenylenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine; 
     p-aminophenol derivatives such as: p-aminophenol, p-methylaminophenol, 3-methyl-4-aminophenol and 1-(5-amino-2-hydroxyphenyl)-ethane-1,2-diol; 
     o-amino derivatives such as: o-aminophenol, 5-methyl-2-aminophenol, 6-methyl-2-aminophenol and 2-amino-5-acetaminophenol; and 
     heterocyclic derivatives such as: 2,4,5,6-tetraaminopyrimidine, and 1-(2-hydroxyethyl)-4,5-diaminopyrazole. 
     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-(2-hydroxyethylamino)anisole and 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine, and 3-(2,4-diaminophenoxy)-1-propanol; 
     m-aminophenols such as: m-aminophenol, 6-hydroxybenzomorpholine, 2-hydroxy-4-aminotoluene, 2-hydroxy-4-(2-hydroxyethylamino)toluene and 2-methyl-m-aminophenol; and 
     heterocyclic derivatives such as: 1-phenyl-3-methyl-5-pyrazolone, 2-amino-3-hydroxypyridine and 6-hydroxyindole. 
     The hair coloring compositions of this invention will contain the couplers of this invention, alone or in combination with other couplers, in an effective coloring amount, generally in an amount of from about 0.01 to about 2.5 weight percent. Other couplers, when present will be present in an amount up to about 2.5 weight percent. The primary intermediate(s) will generally be present in an amount of from about 0.01 to about 3.5 weight percent. The molar ratio of primary intermediate to coupler will generally range from about 5:1 to about 1:5 and be employed in any suitable carrier or vehicle, generally an aqueous or hydroalcoholic solution, preferably an aqueous solution. The carrier or vehicle will generally comprise up to about 40 weight percent. 
     The hair coloring compositions of this invention may contain one or more cationic, anionic or amphoteric surface active agents, perfumes, antioxidants, sequestering agents, thickening agents, alkalizing or acidifying agents, and other dyeing agents. 
     Any suitable peroxide providing agent can be employed in the coloring compositions of this invention, particularly hydrogen peroxide (H 2 O 2 ) or precursors therefor. 
     In general, a first composition of primary intermediate(s) and coupler(s) is prepared and then, at the time of use, the oxidizing agents, such as H 2 O 2 , is admixed therewith until an essentially homogenous composition is obtained which is applied to the hair to be dyed and permitted to remain in contact with the hair for a dyeing effective amount of time, generally for a period of from about 2 to 45, preferably about 2 to 30, minutes, after which the hair is rinsed, shampooed and dried. 
     Dyeing Tests 
     Piedmont hair weighing 700 to 900 mg was used in the tests. A solution of primary intermediate and each coupler was prepared separately according to the following procedure. The concentration of the primary intermediate (PPD=p-phenylenediamine, PAP=p-aminophenol, Pyrazole=2-(4,5-diaminopyrazol-1-yl)ethanol, and PTD=p-toluenediamine) and the coupler was 0.025 M in a base consisting of ethanol 7.85 g, sodium laureth sulfate 10 g, ascorbic acid 0.3 g, EDTA 0.3 g, ammonium hydroxide 8.13 g (28%) and water to 100 g. A solution of the primary intermediate (0.5 mL) and the coupler (0.5 mL) was mixed with 20 volumes hydrogen peroxide (1 mL). The resulting mixture was applied to hair tresses mounted on glass plates and then stored at 40° C. for thirty minutes, washed, shampooed and dried A Minolta spectrophotometer CM-3700d from Minolta Co. is used. Color space is CIE L*a*b* and illuminant is D65 daylight with 10° observer. The color space, L* indicates lightness and a* and b* are the chromaticity coordinates. +a* is the red direction, −a* direction is the green direction, +b* is the yellow direction and −b* is the blue direction. The results are shown in Tables 1 and 2. Reference couplers 5-amino-2-methylphenol (Reference A) and 5-(2-hydroxyethylamino)-2-methylphenol (Reference B) were employed for comparison purposes. 
     
       
         
               
             
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Dyeing results of 2-methyl-5-aminophenol analogs with PAP, PPD and Pyrazole 
               
             
          
           
               
                   
                 Primary Intermediate 
                   
               
             
          
           
               
                 Ex. 
                   
                 HPLC 
                 PAP 
                 PPD 
                 Pyrazole 
                 PTD 
               
             
          
           
               
                 No. 
                 Structure 
                 Purity 
                 L* 
                 a* 
                 b* 
                 L* 
                 a* 
                 b* 
                 L* 
                 a* 
                 b* 
                 L* 
                 a* 
                 b* 
               
               
                   
               
             
          
           
               
                 Ref. A 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 53.57 
                 24.4 
                 32.14 
                 32.82 
                 18.57 
                 0.91 
                 44.69 
                 41.21 
                 33.32 
               
               
                   
               
               
                 Ref. B 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 58.86 
                 22.18 
                 29.18 
                 44.44 
                 11.61 
                 6.14 
                 51.21 
                 33.44 
                 28.51 
               
               
                   
               
               
                 38 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 94 
                 61.42 
                 20.82 
                 28.2 
                 42.39 
                 11.54 
                 3.87 
                 50.29 
                 33.77 
                 27.21 
               
               
                   
               
               
                 39 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 91 
                 60.03 
                 20.18 
                 28.37 
                 39.79 
                 12.64 
                 6.43 
                 49.69 
                 34.1 
                 28.95 
               
               
                   
               
               
                 40 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 94 
                 65 
                 9.15 
                 23.59 
                 47.3 
                 6.21 
                 8.43 
                 56.51 
                 25.35 
                 21.79 
               
               
                   
               
               
                 41 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 91 
                 60.23 
                 18.02 
                 26.91 
                 40.69 
                 8.99 
                 4.95 
                 47.78 
                 31.75 
                 27.01 
               
               
                   
               
               
                 42 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 100 
                 58.74 
                 16.49 
                 25.38 
                 42.57 
                 8.65 
                 7.44 
                 52.38 
                 29.17 
                 25.12 
               
               
                   
               
               
                 43 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 100 
                 64.66 
                 16.01 
                 27.78 
                 42.32 
                 9.02 
                 5.1 
                 52.99 
                 31.18 
                 22.54 
               
               
                   
               
               
                 44 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 90 
                 58.65 
                 19.9 
                 26.88 
                 45.61 
                 10.88 
                 6.76 
                 50.64 
                 32.76 
                 28.45 
               
               
                   
               
               
                 45 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 90 
                 61.85 
                 16.24 
                 24.96 
                 40.89 
                 8.63 
                 2.6 
                 50.18 
                 30.87 
                 23.48 
               
               
                   
               
               
                 46 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 64.33 
                 18.09 
                 26.53 
                 44.24 
                 8.46 
                 6.6 
                 55.29 
                 27.94 
                 25.08 
               
               
                   
               
               
                 47 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 93 
                 58.16 
                 17.39 
                 25.01 
                 39.14 
                 10.91 
                 3.72 
                 47.56 
                 32.7 
                 27.74 
                 47.41 
                 9.15 
                 5.57 
               
               
                   
               
               
                 48 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 92 
                 64.66 
                 15.72 
                 25.59 
                 45.33 
                 8.45 
                 5.35 
                 57.2 
                 27.36 
                 24.05 
               
               
                   
               
               
                 49 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 61.19 
                 18.02 
                 26.53 
                 47.03 
                 9.84 
                 5.49 
                 56.29 
                 29.56 
                 26.05 
               
               
                   
               
               
                 50 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 94 
                 62.26 
                 21.24 
                 27.38 
                 42.55 
                 10.03 
                 5.65 
                 54.05 
                 30.13 
                 25.79 
               
               
                   
               
               
                 51 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 62.05 
                 17.69 
                 25.32 
                 44.12 
                 8.47 
                 6.06 
                 56.5 
                 27.3 
                 24.5 
               
               
                   
               
               
                 52 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 96 
                 60.47 
                 13.36 
                 23.54 
                 44.96 
                 8.75 
                 5.76 
                 51.05 
                 27.55 
                 22.88 
               
               
                   
               
               
                 53 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 94 
                 62.67 
                 17.53 
                 25.75 
                 46.16 
                 8.65 
                 4.59 
                 51.54 
                 32.8 
                 24.98 
               
               
                   
               
               
                 54 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 96 
                 59.01 
                 16.06 
                 25.72 
                 42.5 
                 7.95 
                 3.09 
                 49.7 
                 29.66 
                 26.4 
                 43.95 
                 9.96 
                 1.56 
               
               
                   
               
               
                 55 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 65.5 
                 11.27 
                 25.17 
                 44.75 
                 6.28 
                 7.43 
                 51.67 
                 24.27 
                 21.51 
               
               
                   
               
               
                 56 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 93 
                 63.11 
                 17.17 
                 27.33 
                 43.95 
                 8.11 
                 5.3 
                 54.97 
                 28.57 
                 23.1 
               
               
                   
               
               
                 57 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 96 
                 61.69 
                 18.3 
                 26.92 
                 42.89 
                 7.65 
                 5.84 
                 53.28 
                 29.48 
                 22.22 
               
               
                   
               
               
                 58 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 91 
                 66.29 
                 12.44 
                 24.57 
                 45.87 
                 6.2 
                 7.47 
                 53.42 
                 25.42 
                 21.06 
               
               
                   
               
               
                 59 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 89 
                 59.44 
                 17.34 
                 26.33 
                 39.41 
                 9.98 
                 4.52 
                 46.57 
                 33.89 
                 23.23 
               
               
                   
               
               
                 60 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 93 
                 65.54 
                 15.3 
                 26.2 
                 45.98 
                 8.1 
                 5.29 
                 55.16 
                 30.07 
                 23.42 
               
               
                   
               
               
                 61 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 93 
                 65.91 
                 10.67 
                 22.06 
                 44.14 
                 7.17 
                 6.84 
                 56.47 
                 25.88 
                 21.37 
               
               
                   
               
               
                 62 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 90 
                 60.61 
                 11.37 
                 22.23 
                 48.98 
                 7.98 
                 5.73 
                 53.75 
                 28.31 
                 23.92 
               
               
                   
               
               
                 63 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 92 
                 65.15 
                 10.9 
                 23.68 
                 44.83 
                 5.63 
                 5.49 
                 54.21 
                 27.3 
                 19.8 
               
               
                   
               
               
                 64 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 94 
                 67.75 
                 7.32 
                 22.18 
                 49.94 
                 4.97 
                 8.45 
                 57.68 
                 23.54 
                 19.82 
               
               
                   
               
               
                 65 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 59.59 
                 21.6 
                 28.99 
                 41.96 
                 15.47 
                 5.28 
                 48.77 
                 33.3 
                 28.32 
                 38.92 
                 12.73 
                 0.35 
               
               
                   
               
               
                 66 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 96 
                 61.47 
                 15.49 
                 25.49 
                 38.35 
                 15.18 
                 2.6 
                 47.58 
                 36.32 
                 29.09 
                 43.31 
                 12.19 
                 −0.99 
               
               
                   
               
               
                 67 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 91 
                 63.49 
                 9.25 
                 21.81 
                 47.21 
                 7.88 
                 7.01 
                 52.23 
                 22.76 
                 21.51 
               
               
                   
               
               
                 68 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 65.00 
                 9.10 
                 22.34 
                 47.90 
                 6.53 
                 8.35 
                 51.56 
                 21.53 
                 20.40 
               
               
                   
               
               
                 69 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 88 
                 60.53 
                 6.19 
                 17.29 
                 44.15 
                 6.51 
                 7.17 
                 47.14 
                 19.74 
                 18.17 
               
               
                   
               
               
                 70 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 99 
                 60.69 
                 10.24 
                 20.55 
                 43.07 
                 9.97 
                 5.57 
                 48.65 
                 26.08 
                 22.34 
               
               
                   
               
               
                 71 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 91 
                 62.71 
                 7.04 
                 19.18 
                 47.22 
                 6.90 
                 7.20 
                 52.06 
                 20.48 
                 19.06 
               
               
                   
               
               
                 72 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 89 
                 67.53 
                 6.04 
                 21.25 
                 48.49 
                 5.32 
                 8.62 
                 54.24 
                 17.76 
                 17.66 
               
               
                   
               
               
                 73 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 88 
                 64.01 
                 6.12 
                 19.64 
                 44.02 
                 6.54 
                 7.53 
                 52.79 
                 20.12 
                 19.15 
               
               
                   
               
               
                 74 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 90 
                 59.65 
                 7.88 
                 19.65 
                 42.61 
                 12.19 
                 3.64 
                 45.90 
                 28.99 
                 23.95 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Hair dye compositions 
               
             
          
           
               
                 Ex. No. 
                 Coupler 
                 Primary Intermediate 
                 Color obtained 
               
               
                   
               
               
                 Ref. A 
                 5-Amino-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 Ref. B 
                 5-(2-Hydroxy-ethylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 75 
                 2-Methyl-5-[(pyridin-3-ylmethyl)-amino]-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 76 
                 3-[(3-Hydroxy-4-methyl-phenylamino)-methyl]-benzonitrile 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 77 
                 5-(2-Fluoro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 78 
                 5-(3-Fluoro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 79 
                 5-(2,3-Difluoro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 80 
                 5-(2,4-Difluoro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 81 
                 5-(2-Methoxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4,-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 82 
                 5-(2-Hydroxy-3-methyoxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 83 
                 2-Methyl-5-(3,4,5-trimethoxy-benzylamino)-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 84 
                 5-(2-Hydroxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 85 
                 2-Methyl-5(2,3,4-trimethoxy-benzylamino)-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 86 
                 5-(2,3-Dimethoxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 87 
                 5-(2,5-Dimethoxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 88 
                 5-(2-Chloro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 89 
                 5-(3-Chloro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 90 
                 5-(3-Methoxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 91 
                 5-(2-Hydroxy-5-methoxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 92 
                 5-[(2,3-Dihydro-benzo[1,4]dioxin-6-ylmethyl)-amino]-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 93 
                 5-(3-Hydroxy-4-methyl-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 94 
                 2-Methyl-5(4-trifluoromethyl-benzylamino)-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 95 
                 5-(4-Methoxy-3-methyl-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 96 
                 5-(3,5-Dimethyl-4-hydroxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 97 
                 5-(3,4-Difluoro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 98 
                 5-(4-Methoxy-2,5-dimethyl-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 99 
                 5-(2,4-Dimethoxy-3-methyl-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 100 
                 2-Methyl-5(2,4,5-trimethoxy-benzylamino)-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 101 
                 5-(4-Methoxy-2,3-dimethyl-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 102 
                 2-Methyl-5-[(1H-pyrrol-2-ylmethyl)-amino]-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 103 
                 5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 104 
                 5-Benzylamino-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 105 
                 5-(4-Fluoro-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 106 
                 5-(4-Methoxy-benzylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 107 
                 2-Methyl-5-[(thiophen-2-ylmethyl)-amino]-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 108 
                 2-Methyl-5-[(5-methyl-thiophen-2-ylmethyl)-amino]-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 109 
                 5-[(Benzo[1,3]dioxol-5-ylmethyl)-amino]-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 110 
                 2-Methyl-5-(4-nitro-benzylamino)-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 111 
                 5-[(5-Bromo-furan-2-ylmethyl)-amino]-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                   
               
             
          
         
       
     
     EXAMPLE 112 
     The following compositions shown in Table 3 were used for dyeing Piedmont hair. The dyeing solution was mixed with 100 g 20 volume hydrogen peroxide. The resulting mixture was applied to the hair and permitted to remain in contact with the hair for 30 minutes. This dyed hair was then shampooed and rinsed with water and dried. The results are shown in Tables 4, 5 and 6. A Minolta spectrophotometer CM-3700d from Minolta Co. is used. Color space is CIE L*a*b* and illuminant is D65 daylight with 10° observer. 
     
       
         
               
             
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Composition for the Dyeing Solution 
               
             
          
           
               
                   
                 Ingredients 
                 Weight (%) 
               
               
                   
                   
               
               
                   
                 Cocamidopropyl betaine 
                 17.00  
               
               
                   
                 Monoethanolamine 
                 2.00 
               
               
                   
                 Oleic Acid 
                 0.75 
               
               
                   
                 Citric Acid 
                 0.10 
               
               
                   
                 Ammonium hydroxide 
                 5.00 
               
               
                   
                 Behentrimonium chloride 
                 0.50 
               
               
                   
                 Sodium sulfite 
                 0.10 
               
               
                   
                 EDTA 
                 0.10 
               
               
                   
                 Erythorbic acid 
                 0.40 
               
               
                   
                 Ethoxydiglycol 
                 3.50 
               
               
                   
                 C11-15 Pareth-9 (Tergitol 15-S-9) 
                 1.00 
               
               
                   
                 C12-15 Pareth-3 (Neodol 25-3) 
                 0.50 
               
               
                   
                 Isopropanol 
                 4.00 
               
               
                   
                 Propylene glycol 
                 2.00 
               
               
                   
                 p-aminophenol 
                 5 mmole 
               
               
                   
                 Coupler (of this invention or prior art) 
                 5 mmole 
               
               
                   
                 Water 
                 qs to 100.00 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Coupling of p-aminophenol with Compounds 1, 2 and 3 
               
             
          
           
               
                   
                 Coupler Compound 
                 L* 
                 a* 
                 b* 
               
               
                   
                   
               
               
                   
                 1 
                 44.55 
                 28.05 
                 29.08 
               
               
                   
                 2 
                 48.08 
                 24.35 
                 29.63 
               
               
                   
                 3# 
                 56.93 
                 20.09 
                 27.51 
               
               
                   
                   
               
               
                   
                 #Half of the concentration was used due to low solubility in dye base tested.  
               
             
          
         
       
     
     Surprisingly, dye-uptake of Compound 1 on Piedmont hair when coupled with p-aminophenol is almost identical to that of the prior art compound 2-methyl-5-N-hydroxyethylaminophenol even though the size of Compound 1 is bigger than the prior art compound (Table 5). In addition, the Compound 1 is a two-ring system, while the prior art compound is a one-ring system. Compound 2 colors hair weaker (48.08 vs. 44.55) and less bright (a*24.35 vs. 28.05) than Compound 1 (Table 5). 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Coupling of p-aminophenol with Synthesis Compounds 1 and 2 
               
             
          
           
               
                   
                 Coupler Compound 
                 L* 
                 a* 
                 b* 
               
               
                   
                   
               
               
                   
                 1 
                 44.55 
                 28.05 
                 29.08 
               
               
                   
                 Prior Art ++   
                 46.44 
                 28.22 
                 29.78 
               
               
                   
                 2 
                 48.08 
                 24.35 
                 29.63 
               
               
                   
                   
               
               
                   
                   ++ 2-methyl-5-N-hydroxyethylaminophenol  
               
             
          
         
       
     
     Wash Fastness Test 
     Piedmont hair dyed with p-aminophenol and Compound 1 was immersed in 10% Herbal Essences™ shampoo and shaken for 6 hours at room temperature. The results are shown in Table 6. Wash fastness test has shown that overall color change represented by ΔE is 7.58. 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Wash Fastness Test of Dyes with p-aminophenol 
               
             
          
           
               
                   
                 Before Shampooing 
                 After 6 hr Shampooing 
                   
               
             
          
           
               
                 Coupler 
                 L* 
                 a* 
                 B* 
                 L* 
                 a* 
                 b* 
                 ΔE 
               
               
                   
               
               
                 Compound 1 
                 47.24 
                 25.58 
                 27.78 
                 45.16 
                 18.88 
                 24.91 
                 7.58 
               
               
                   
               
             
          
         
       
     
     
       
           ΔE= {overscore ((Δ L *) 2 +(Δ a *) 2 +(Δ b *) 2 )} 
       
     
     Exemplary combinations of hair coloring components employing a 2-arylaminomethyl-4-aminophenol primary intermediate of formula (1) of this invention are shown in combinations C1 to C126 in Table A. Reading down the columns in Table A, the Xes demonstrate combinations of dyes that can be formulated according to the present invention. For example, in Combination No. 1 in Column 4 of Table A, a 2-arylaminomethyl-4-aminophenol of formula (1) of this invention (Row 1 of Table A), wherein R and R 1  are defined hereinbefore, can be combined with p-toluene diamine, and 2-amino-phenol. Especially preferred as the 2-arylaminomethyl-4-aminophenol components in the combinations C1 to C126 of Table A are 4-(5-amino-2-hydroxy-benzylamino)-benzonitrile, 4-amino-2-[(4-hydroxy-phenolamino)-methyl]-phenol, 4-amino-2-[4-hydroxy-2,5-dimethyl-phenyl-amino)-methyl]-phenol and 4-amino-2-(pyridin-3-ylaminomethyl)-phenol. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE A 
               
               
                   
               
               
                 DYE COMBINATIONS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Structure 
                 IUPAC Name 
                 Name 
                 C1 
                 C2 
                 C3 
                 C4 
                 C5 
                 C6 
                 C7 
                 C8 
                 C9 
                 C10 
                 C11 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5-Arylmethylalamino-2- methylphenolphenol 
                 5-Arylmethylalamino-2- methylphenolphenol 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl-benzene-1,4- diamine 
                 p-Toluene-diamine 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Benzene-1,4-diamine 
                 p-Phenylene-diamine 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-[(4-Amino-phenyl)- (2-hydroxy-ethyl)- amino]-ethanol 
                 N,N-Bis(2- hydroxyethyl)-p- phenylene-diamine 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amino-phenol 
                 p-Aminophenol 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amino-3-methyl- phenol 
                 3-Methyl-p- aminophenol 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Amino-phenol 
                 p-Aminophenol 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Benzene-1,3-diol 
                 Resorcinol 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl-benzene-1,3- diol 
                 2-Methyl-resorcinol 
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Naphthalene-1-ol 
                 1-Naphthol 
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl-naphthaien- 1-ol 
                 2-Methyl-1-naphthol 
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-(2,4-Diamino- phenoxy)-ethanol 
                 2,4-Diamino- phenoxyethanol 
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Benzene-1,3-diamine 
                 m-Phenylenediamine 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 3-Amino-phenol 
                 m-Aminophenol 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 5-Amino-2-methyl- phenol 
                 2-Hydroxy-4- aminotoluene 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-(4,5-Diamino- pyrazol-1-yl)-ethanol 
                 1-Hydroxyethyl-4,5- diamino-pyrazole 
               
               
                   
               
               
                   
               
             
          
           
               
                 Structure 
                 C12 
                 C13 
                 C14 
                 C15 
                 C16 
                 C17 
                 C18 
                 C19 
                 C20 
                 C21 
                 C22 
                 C23 
                 C24 
                 C25 
                 C26 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
               
               
                 Structure 
                 C27 
                 C28 
                 C29 
                 C30 
                 C31 
                 C32 
                 C33 
                 C34 
                 C35 
                 C36 
                 C37 
                 C38 
                 C39 
                 C40 
                 C41 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
               
               
                 Structure 
                 C42 
                 C43 
                 C44 
                 C45 
                 C46 
                 C47 
                 C48 
                 C49 
                 C50 
                 C51 
                 C52 
                 C53 
                 C54 
                 C55 
                 C56 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
               
               
                 Structure 
                 C57 
                 C58 
                 C59 
                 C60 
                 C61 
                 C62 
                 C63 
                 C64 
                 C65 
                 C66 
                 C67 
                 C68 
                 C69 
                 C70 
                 C71 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
               
               
                 Structure 
                 C72 
                 C73 
                 C74 
                 C75 
                 C76 
                 C77 
                 C78 
                 C79 
                 C80 
                 C81 
                 C82 
                 C83 
                 C84 
                 C85 
                 C86 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
               
               
                 Structure 
                 C87 
                 C88 
                 C89 
                 C90 
                 C91 
                 C92 
                 C93 
                 C94 
                 C95 
                 C96 
                 C97 
                 C98 
                 C99 
                 C100 
                 C101 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                   
               
               
                 Structure 
                 C102 
                 C103 
                 C104 
                 C105 
                 C016 
                 C017 
                 C018 
                 C019 
                 C110 
                 C111 
                 C112 
                 C113 
                 C114 
                 C115 
                 C116 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                   
               
             
          
           
               
                 Structure 
                 C117 
                 C118 
                 C119 
                 C120 
                 C121 
                 C122 
                 C123 
                 C124 
                 C125 
                 C126 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
                 X 
               
               
                   
               
             
          
         
       
     
     With the foregoing description of the invention, those skilled in the art will appreciate that modifications may be made to the invention without departing from the spirit thereof. Therefore, it is not intended that the scope of the invention be limited to the specific embodiments illustrated and described.