Abstract:
Couplers for hair coloring compositions for oxidative dyeing of hair are compounds of the formula at least one coupler comprising a compound of the formula (1):                            
     wherein R is selected from of C 1  to C 2  alkyl and hydroxyethyl, R 1  and R 2  are each independently selected from the group consisting of C 1  to C 5  alkyl, C 3  to C 6  cycloalkyl, C 1  to C 5  alkoxy, C 1  to C 5  hydroxyalkyl, C 1  to C 5  hydroxyalkoxy, or R 1  and R 2  together with the carbon atom to which they are attached form a C 3  to C 6  cycloalkyl group.

Description:
FIELD IF 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 modem 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-methyl-phenol. 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 5-hydroxyethylamino-2-methyl-phenol, 5-alkylamino-2-methyl-phenol and 5-amino-2-methyl-phenol 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  and R 2  are each independently selected from a C 1  to C 5  alkyl, C 1  to C 3  alkoxy , C 1  to C 5  hydroxyalkyl, C 1  to C 5  hydroxyalkoxy, C 3  to C 6  cycloalkyl, or R 1  and R 2 together with the carbon atom to which they are attached form a C 3  to C 6  cycloalkyl group. 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 5-amino-2-methyl-phenol. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Preferred coupler compounds of this invention are those of formula (1):                           
     wherein R is a methyl group, and R 1  and R 2  are as defined hereinbefore. 
     Especially preferred couplers of this invention are the following compounds: 
     5-isopropylamino-2-methyl-phenol, 
     5-(1-cyclopropyl-ethylamino) 2-methyl-phenol, 
     5-cyclobutylamino-2-methyl-phenol, 
     5-cyclopentylamino-2-methyl-phenol, 
     5-cyclohexylamino-2-methyl-phenol, 
     5-(2-methoxy-1-methyl-ethylamino)-2-methyl-phenol, 
     5-(1,2-dimethyl-propylamino)-2-methyl-phenol, 
     5-(1-ethyl-propylamino)-2-methyl-phenol, 
     2-methyl-5-(1-methyl-butylamino)-phenol, and 
     5-sec-butylamino-2-methyl-phenol. 
     The novel coupler compounds of formula (1) of this invention are readily prepared by a reaction of an aminophenol of formula (2) with an appropriate ketone 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 R 2  are as defined hereinbefore and R is preferably a methyl group, R 1  and R 2  are preferably C 1  to C 5  alkyl, C 3  to C 6  cycloalkyl or together with the carbon atom to which they are joined form a C 3  to C 6  cycloalkyl group. 
     A sample synthesis procedure is as follows. A ketone (3) (0.3 mmole) is treated with an excess of an aminophenol compound (2) (44.3 mg, 1.2 equiv. based on R being methyl) in 1% AcOH-DCE (dichloroethane) (4 mL). The mixture is agitated in a reaction vessel for about 1 hr at room temperature and then sodium triacetoxyborohydride (127 mg, 0.6 mmole) is added. The mixture is agitated for about 18 hr and then Argonaut PS-MB aldehyde (100 mg, 1.26 mmole/g loading) is added. The mixture is agitated for about 1 hr, filtered and rinsed with anhydrous DCE (2 mL). To the filtrate is added water (2 mL), shaken and water is 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 (1). The product is subjected to one or more of analysis by analytical HPLC, identification by MS and characterization by  1 H NMR. 
     Compounds were prepared according to the foregoing synthesis procedure. The compounds prepared were as follows: 
     5-isopropylamino-2-methyl-phenol, 
     5-(1-cyclopropyl-ethylamino)-2-methyl-phenol, 
     5-cyclobutylamino-2-methyl-phenol, 
     5-cyclopentylamino-2-methyl-phenol, 
     5-cyclohexylamino-2-methyl-phenol, 
     5-(2-methoxy-1-methyl-ethylamino)-2-methyl-phenol, 
     5-(1,2-dimethyl-propylamino)-2-methyl-phenol, 
     5-(1-ethyl-propylamino)-2-methyl-phenol, 
     2-methyl-5-(1-methyl-butylamino)-phenol, and 
     5-sec-butylamino-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. 
     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, 
     Examples of such other suitable primary intermediates include: 
     p-phenylenediamine derivatives such as: benzene-1,4-diamine (commonly known as p-phenylenediamine), 2-methyl-benzene-1,4-diamine (commonly known as 2-methyl-p-phenylenediamine), 2-chloro-benzene-1,4-diamine, N-phenyl-benzene-1,4-diamine, N-(2-ethoxyethyl)benzene-1,4-diamine, 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol (commonly known as N,N-bis(2-hydroxyethyl)-p-phenylenediamine), (2,5-diamino-phenyl)-methanol, 1-(2,5-diamino-phenyl)-ethanol, 2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine, 2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine, 1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine, 1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol, N 4 ,N 4 ,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine, 1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine, N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine, 2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-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-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol, 2-[(4-amino-3-methyl-phenyl)-(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: 4-amino-phenol (commonly known as p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyl-phenol, 4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-[(2-hydroxy-ethylamino)-methyl]-phenol, 4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid, 1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, 4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)phenol, and 4-amino-2-fluoro-phenol; 
     o-aminophenol derivatives such as: 2-amino-phenol (commonly known as o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide (commonly known as 2-amino-5-acetaminophenol), and 2-amino4-methyl-phenol; and 
     heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonly known as 2,4,5,6-tetraaminopyrimidine), 1-methyl-1H-pyrazole-4,5-diamine, 2-(4,5-diamino-1H-pyrazol-1-yl)ethanol (commonly known as 1-(2-hydroxyethyl)-4,5-diaminopyrazole), N 2 ,N 2 -dimethyl-pyridine-2,5-diamine, 2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol, 6-methoxy-N2-methyl-pyridine-2,3-diamine, 2,5,6-triaminopyrimidin-4(1H)-one, 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. 
     The novel coupler compounds of this invention may be used alone or in combination with other suitable couplers along with the suitable primary intermediates in hair coloring compositions or systems of this invention. 
     Suitable other couplers include, for example: 
     phenols, resorcinol and naphthol derivatives such as: naphthalene-1,7-diol, benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol, naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-1,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonic acid, 2-isopropyl-5-methylphenol, 1,2,3,4-tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol, 4-hydroxy-naphthalene-1-sulfonic acid, benzene-1,2,3-triol, naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-diol, 4,6-dichlorobenzene-1,3-diol, and 2,3-dihydroxy-[1,4]naphthoquinone; 
     m-phenylenediamines such as: 2,4-diaminophenol, benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol, 2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 2-methyl-benzene-1,3-diamine, 2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol, 4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine, 2-(2,4-diamino-phenyl)-ethanol, 2-(3-amino4-methoxy-phenylamino)-ethanol, 4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-acetic acid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, 4-ethoxy-6-methyl-benzene-1,3-diamine, 2-(2,4-diamino-5-methyl-phenoxy)-ethanol, 4,6-dimethoxy-benzene-1,3-diamine, 2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol, 3-(2,4-diamino-phenoxy)-propan-1-ol, N-[3-(dimethylamino)phenyl]urea, 4-methoxy-6-methylbenzene-1,3-diamine, 4-fluoro-6-methylbenzene-1,3-diamine, 2-({3-[(2-hydroxyethyl)amino]-4,6dimethoxyphenyl}amino)ethanol, 3-(2,4-diaminophenoxy)-propane-1,2-diol, 2-[2-amino4-(methylamino)phenoxy]ethanol, 2-[(5-amino-2-ethoxy-phenyl)-(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: 3-amino-phenol, 2-(3-hydroxy4-methyl-phenylamino)-acetamide, 2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol, 3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 5-amino-2-(2-hydroxy-ethoxy)-phenol, 2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol, 5-amino4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol, 5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol, 3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol, 3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol, 5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol, 5-[(3-hydroxypropyl)amino]-2-methylphenol, 3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol, and 3-[(2-hydroxyethyl)amino]-2-methylphenol; and 
     heterocyclic derivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol, 4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol, 2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol, 2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol, 5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine, 1,3-benzodioxol-5-amine, 2,6-bis(2-hydroxyethoxy)-3,5-diaminopyridine, 1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol, 1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 6-bromo-1,3-benzodioxol-5-ol; 2-aminopyridin-3-ol, pyridine-2,6-diamine, 3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol, 5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol, 1H-indole-2,3-dione, indoline-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-benzene-1,4-diamine, benzene-1,4-diamine, 1-(2,5-diamino-phenyl)-ethanol, 2-(2,5-diamino-phenyl)-ethanol, N-(2-methoxyethyl)benzene-1,4-diamine, 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 1-(2,5-diaminophenyl)ethane-1,2-diol, 2-thien-2-ylbenzene-1,4-diamine, 2-thien-3-ylbenzene-1,4-diamine, and 2-(aminomethyl)benzene-1,4-diamine 
     p-aminophenol derivatives such as 4-amino-phenol, 4-methylamino-phenol, 4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol, 1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, and 4-amino-2-(aminomethyl)phenol; 
     o-aminophenol derivatives such as: 2-amino-phenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; 
     heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine, 1-methyl-1H-pyrazole-4,5-diamine, 2-(4, 5-diamino-1H-pyrazol-1-yl)ethanol, and N 2 ,N 2 -dimethyl-pyridine-2,5-diamine. 
     Preferred couplers include: 
     phenols, resorcinol and naphthol derivatives such as: naphthalene-1,7-diol, benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol, naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and 2-isopropyl-5-methylphenol; 
     m-phenylenediamines such as: benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol, 4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine, 2-(3-amino4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol; 
     m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol; and 
     heterocyclic derivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol, 4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,3-benzodioxol-5-ol, 1,3-benzodioxol-5-amine, 1H-indol-4-ol, 1H-indole-5,6-diol, 1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 1H-indole-2,3-dione, pyridine-2,6-diamine, and 2-aminopyridin-3-ol. 
     Most preferred primary intermediates include: 
     p-phenylenediamine derivatives such as: 2-methyl-benzene-1,4-diamine, benzene-1,4-diamine, 2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol, 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 1-(2,5-diaminophenyl)ethane-1,2-diol, 2-thien-2-ylbenzene-1,4-diamine, 2-thien-3-ylbenzene-1,4-diamine, and 2-(aminomethyl)benzene-1,4-diamine; 
     p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino-phenol, 4-amino-3-methyl-phenol, 1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, and 4-amino-2-(aminomethyl)phenol; 
     o-aminophenols such as: 2-amino-phenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol, and N-(4-amino-3-hydroxy-phenyl)-acetamide; and 
     heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine and 2-(4,5-diamino-1H-pyrazol-1-yl)ethanol. 
     Most preferred couplers include: 
     phenols, resorcinol and naphthol derivatives such as: benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol-1,2-methyl-naphthalen-1-ol, and 2-methyl-benzene-1,3-diol; 
     m-phenylenediamines such as: 2-(2,4-diamino-phenoxy)-ethanol, 2-(3-amino4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol; 
     m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol; and 
     heterocyclic derivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol, 4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, and 1H-indol-6-ol, and 2-aminopyridin-3-ol. 
     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 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. 
    
    
     SYNTHETICS EXAMPLES 1TO 12 
     EXAMPLE 1 
     Preparation of 5-(1-Cyclopropyl-ethylamino)-2-methyl-phenol 
     Cyclopropyl methyl ketone (40.4 mg, 0.48 mmole) was weighed into a 15 mL reaction vessel,To this vessel was added a 1% acetic acid in anhydrous 1,2-dichloroethane solution (4 mL) and 5-amino-2-methyl-phenol (49.3mg, 0.40 mmole). The reaction vessel was shaken at room temperature for 0.5 h. Sodium triacetoxyborohydride (169.9 mg, 0.80 mmole) and a 1% acetic acid in anhydrous 1,2-dichloroethane solution (1 mL) was added and the reaction vessel was shaken at room temperature for 18 h. The reaction was vacuum filtered and rinsed with anhydrous 1,2-dichloroethane (2 mL). The filtrate was washed with water (2×2 mL). The organic phase was dried by filtering through a Chem Elute™ cartridge. The cartridge was rinsed with anhydrous 1,2-dichloroethane (3×2 mL). The resulting solution was evaporated under vacuum and purified on the preparative HPLC to yield compound 2 of Table 1 as its trifluoroacetate (TFA) salt:  1 HNMR (DMSO-d 6 ) δ 9.86 (bs, 1H, OH), 7.13 (d, J=6.9 Hz, 1H), 6.74 (s, 1H), 6.67 (s, 1H), 4.10 (m, 1H), 2.90 (m, 1H), 2.09 (s, 3H), 1.18 (d, J=6.6 Hz, 3H), 0.87 (m, 1H), 0.49 (t, J=8.2 Hz, 2H), 0.27 (d, J=5.9 Hz, 2H). MS calculated for C 12 H 17 NO (M) + : 191. Found: 191. 
     EXAMPLES 2 TO 10 
     With the substitution of the appropriate ketone for cyclopropyl methyl ketone in the synthesis procedure of Example 1 Compounds 1 and 3 to 10 of Table 1 were prepared, namely: 
     5-isopropylamino-2-methyl-phenol, 
     5-cyclobutylamino-2-methyl-phenol, 
     5-cyclopentylamino-2-methyl-phenol, 
     5-cyclohexylamino-2-methyl-phenol, 
     5-(2-methoxy-1-methyl-ethylamino)-2-methyl-phenol, 
     5-(1,2-dimethyl-propylamino)-2-methyl-phenol, 
     5-(1-ethyl-propylamino)-2-methyl-phenol, 
     2-methyl-5-(1-methyl-butylamino)-phenol, and 
     5-sec-butylamino-2-methyl-phenol. 
     EXAMPLES 11 TO 30 
     Dyeing Tests 
     Piedmont hair weighing 700 to 900 mg was used in the test. A solution of the 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 volume 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 CIEL *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-amino2-methyl-phenol (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 
               
             
          
           
               
                   
                 Com- 
                   
                   
                   
                   
                   
                   
               
               
                 Ex. 
                 pound 
                   
                 HPLC 
                 PAP 
                 PPD 
                 Pyrazole 
                 PTD 
               
             
          
           
               
                 No. 
                 No 
                 Structure 
                 Purity 
                 L* 
                 a* 
                 b* 
                 L* 
                 a* 
                 b* 
                 L* 
                 a* 
                 b* 
                 L* 
                 a* 
                 b* 
               
               
                   
               
             
          
           
               
                   
                 Reference A 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 53.57 
                 24.4 
                 32.14 
                 32.82 
                 18.67 
                 0.91 
                 44.69 
                 41.21 
                 33.32 
               
               
                   
               
               
                   
                 Reference B 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                 58.86 
                 22.18 
                 29.18 
                 44.44 
                 11.61 
                 6.14 
                 51.21 
                 33.44 
                 28.51 
               
               
                   
               
               
                 11 
                 1 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 94 
                 62.7 
                 22.81 
                 29.52 
                 45.54 
                 10.9 
                 70.2 
                 47.54 
                 34.95 
                 26.47 
                 45.34 
                 11.85 
                 3.27 
               
               
                   
               
               
                 12 
                 2 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 56.95 
                 10.48 
                 20.00 
                 44.14 
                 11.72 
                 5.34 
                 42.65 
                 26.33 
                 22.05 
                 50.23 
                 8.45 
                 5.61 
               
               
                   
               
               
                 13 
                 3 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 97 
                 57.20 
                 13.56 
                 22.25 
                 40.89 
                 12.19 
                 4.72 
                 44.65 
                 30.70 
                 24.11 
                 49.37 
                 9.31 
                 5.08 
               
               
                   
               
               
                 14 
                 4 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 98 
                 59.39 
                 12.99 
                 22.96 
                 43.61 
                 10.18 
                 5.48 
                 41.38 
                 25.02 
                 20.39 
                 50.83 
                 7.75 
                 8.17 
               
               
                   
               
               
                 15 
                 5 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 97 
                 61.11 
                 9.40 
                 20.31 
                 47.24 
                 7.46 
                 8.05 
                 46.61 
                 23.47 
                 20.63 
                 57.26 
                 5.68 
                 11.05 
               
               
                   
               
               
                 16 
                 6 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 97 
                 59.00 
                 12.95 
                 22.45 
                 42.21 
                 13.01 
                 4.37 
                 44.51 
                 27.26 
                 22.83 
                 52.03 
                 8.29 
                 6.32 
               
               
                   
               
               
                 17 
                 7 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 95 
                 63.06 
                 8.02 
                 20.68 
                 43.93 
                 7.65 
                 5.51 
                 51.11 
                 25.16 
                 22.92 
                 53.33 
                 6.35 
                 8.35 
               
               
                   
               
               
                 18 
                 8 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 96 
                 60.52 
                 7.03 
                 16.90 
                 46.26 
                 8.56 
                 6.19 
                 50.40 
                 21.72 
                 21.53 
                 54.02 
                 8.41 
                 8.19 
               
               
                   
               
               
                 19 
                 9 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 100 
                 64.26 
                 8.18 
                 20.97 
                 47.30 
                 8.66 
                 6.88 
                 51.36 
                 25.17 
                 23.34 
                 51.97 
                 6.50 
                 7.00 
               
               
                   
               
               
                 20 
                 10 
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 93 
                 61.16 
                 7.29 
                 18.72 
                 45.05 
                 9.57 
                 5.51 
                 45.87 
                 26.52 
                 22.67 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Hair Colors derived from Orange Couplers and various Primary Intermediates 
               
             
          
           
               
                 Ex. 
                   
                   
                   
                   
               
               
                 No. 
                 Compound 
                 Coupler 
                 Primary Intermediate 
                 Color obtained 
               
               
                   
               
               
                 A1 
                   
                 5-Amino-2-methyl-phenol (Reference A) 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 A2 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 A3 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 B1 
                   
                 5-(2-Hydroxy-ethylamino)-2-methyl-phenol (Reference B) 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 B2 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 B3 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 21a 
                 1 
                 5-Isopropylamino-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 21b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 21c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 21d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 22a 
                 2 
                 5-(1-Cyclopropyl-ethylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 22b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 22c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 22d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 23a 
                 3 
                 5-Cyclobutylamino-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 23b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 23c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 23d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 24a 
                 4 
                 5-Cyclopentylamino-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 24b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 24c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 24d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 24a 
                 5 
                 5-Cyclohexylamino-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 25b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 25c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 25d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 26a 
                 6 
                 5-(2-Methoxy-1-methyl-ethylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 26b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 26c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 26d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 27a 
                 7 
                 5-(1,2-Dimethyl-propylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 27b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 27c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 27d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 28a 
                 8 
                 5-(1-Ethyl-propylamino)-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 28b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 28c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 28d 
                   
                   
                 2-Methyl-benzene-1,4-diamine 
                 Violet 
               
               
                 29a 
                 9 
                 2-Methyl-5-(1-methyl-butylamino)-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 29b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 29c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                 30a 
                 10  
                 5-sec-Butylamino-2-methyl-phenol 
                 Benzene-1,4-diamine 
                 Violet 
               
               
                 30b 
                   
                   
                 4-Amino-phenol 
                 Orange 
               
               
                 30c 
                   
                   
                 2-(4,5-Diamino-pyrazol-1-yl)-ethanol 
                 Orange red 
               
               
                   
               
             
          
         
       
     
     Exemplary combinations of hair coloring components employing a novel orange coupler of formula (1) of this invention, where R, R 1  and R 2  are as defined hereinbefore, 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. C1 in Column 4 of Table A, a novel coupler of Formula (1) of this invention (Row 1 of Table A) 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 5-isopropylamino-2-methyl-phenol, 5-(l -cyclopropyl-ethylamino)-2-methyl-phenol, 5cyclobutyl-amino-2-methyl-phenol and 5-(2-methoxy-l-methyl-ethylamino)-2-methyl-phenol. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE A 
               
               
                   
               
               
                 DYE COMBINATIONS 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Structure 
                 IUPAC Name 
                 Name 
                 C1 
                 C2 
                 C3 
                 C4 
                 C5 
                 C6 
                 C7 
                 C8 
                 C9 
                 C10 
                 C11 
               
               
                   
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                   
                   
                 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 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-[(4-Amino-phenyl)- (2-hydroxy-ethyl)- amino]-ethanol 
                 N,N-Bis(2- hydroethyl)-p- phenylene-diamine 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amine-phenol 
                 p-Aminophenol 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 4-Amino-3-methyl- phenol 
                 3-Methyl-p- aminophenol 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Amino-phenol 
                 o-Aminophenol 
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Benzene-1,3-diol 
                 Resorcinol 
                   
                 X 
                   
                   
                   
                   
                   
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl-benzene-1,3 diol 
                 2-Methyl-resorcinol 
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 Naphthalon-1-ol 
                 1-Naphithol 
                   
                   
                   
                 X 
               
               
                   
               
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
                 2-Methyl-naphthalon- 1-ol 
                 2-Methyl-1-naphithol 
                   
                   
                   
                   
                 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- pyraxol-1-yl)-ethanol 
                 1-Hydroxyethyl-4,5- diaminO-pyraxole 
               
               
                   
               
             
          
           
               
                 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 
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                 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 
                 C106 
                 C107 
                 C108 
                 C109 
                 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 
               
               
                   
               
             
          
           
               
                   
                 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.