Abstract:
Couplers for hair coloring compositions for oxidative dyeing of hair are compounds of the formula (1):  
                         
 
     wherein X is selected from halogen and R 5 SO 4 ; R, R 1 , R 2  and R 5  are each individually selected from C 1  to C 22  alkyl and C 1  to C 22  mono or dihydroxyalkyl and R 3  and R 4  are individually selected from C 1  to C 6  alkyl groups, C 1  to C 6  hydroxyalkyl, C 1  to C 6  alkoxy, C 1  to C 6  aminoalkyl or R 3  and R 4  together form a C 1  to C 5  alkylene group.

Description:
FIELD OF THE INVENTION  
         [0001]    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  
         [0002]    Coloration of hair is a procedure practiced from antiquity employing a variety of means. In modern times, the most extensively used method employed to color hair is to color hair by an oxidative dyeing process employing hair coloring systems utilizing one or more oxidative hair coloring agents in combination with one or more oxidizing agents.  
           [0003]    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.  
           [0004]    A wide variety of primary intermediates and couplers have been employed in such oxidative hair coloring systems and compositions. Among the primary intermediates employed there may be mentioned p-phenylenediamine, p-toluenediamine, p-aminophenol, 4-amino-3-methylphenol, and as couplers there may be mentioned resorcinol, 2-methylresorcinol, 3-aminophenol, and 5-amino-2-methylphenol. A majority of the shades have been produced with dyes based on p-phenylenediamine.  
           [0005]    DE 4422603 describes oxidative hair dyes based on 4,5-diamininopyrazoles and m-phenylenediamine derivatives. Especially (3-dimethylamino-phenyl)-urea couples with 4,5-diaminopyrazole to provide a blue color. However, the intensity of the blue is not very strong probably due to the solubility of the compound. Therefore, there is a need for new couplers for use in oxidative hair dyeing compositions and systems to increase dye-uptake, resulting in strong blue coloration.  
         BRIEF SUMMARY OF THE INVENTION  
         [0006]    This invention provides novel couplers of the formula (1):  
                         
 
           [0007]    wherein X is selected from halogen and R 5 SO 4  where the halogen is preferably Cl, Br or I; R, R 1 , R 2  and R 5  are each individually selected from C 1  to C 22  alkyl and C 1  to C 22  mono or dihydroxyalkyl and R 3  and R 4  are each individually selected from C 1  to C 6  alkyl, C 1  to C 6  hydroxyalkyl, C 1  to C 6  alkoxy, C 1  to C 6  aminoalkyl or R 3  and R 4  together form a C 1  to C 5  alkylene group. Preferably X is Cl, Br, I and R 5 SO 4  where R 5  is C 1  to C 4  alkyl, more preferably methyl; and preferably R, R 1 , R 2 , R 3  and R 4  are each individually C 1  to C 4  alkyl, and more preferably methyl. 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. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION  
       [0008]    Preferred coupler compounds of this invention are those of formula (1)  
                         
 
         [0009]    wherein X is selected from Cl, Br I and R 5 SO 4  where R 5  is C 1  to C 3  alkyl; and R, R 1 , R 2 , and R 5  are each individually a C 1  to C 3  alkyl group, preferably methyl groups; and R 3  and R 4  are individually selected from C 1  to C 3  alkyl groups, preferably methyl groups.  
         [0010]    Especially preferred couplers of this invention are the following compounds:  
         [0011]    quatererized N-[2-(trimethylamino)ethyl]N′-[3-(dimethylamino)phenyl]urea iodide, chloride, bromide and methyl sulfate salts;  
         [0012]    The novel coupler compounds of formula (1) of this invention are readily prepared according to the following reaction sequence where X, R, R 1 , R 2 , R3, R 4  and R 5  are as defined hereinbefore:  
                         
 
         [0013]    As a example of such synthesis an aminobenzoic acid of formula (2) is subjected to a Curtius rearrngement with diphenylphosphoryl azide (DPPA) and triethylamine (Et 3 N) in toluene to give the isocyanate of formula (3). Reaction of this isocyanate with a disubstituted ethylene diamine (H 2 N—CH 2 —CH 2 —N—R 1 ,R 2 ) produces the urea compound of formula (4). Reaction of this urea compound with the quaternization reagent R-X produces the quaternized urea compounds of formula (1).  
       Synthesis Examples 1 to 10  
       [0014]    Employing the appropriate aminobenzoic acid, disubstituted ethylene diamine and R-X reagent the following compounds are prepared according to the aforedescribed synthesis:  
         [0015]    quaternized iodide salt of N-[2-(trimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0016]    quaternized chloride salt of N-[2-(dimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0017]    quaternized chloride salt of N-[2-(trimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0018]    quaternized bromide salt of N-[2-(triimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0019]    quaternized methyl sulfate salt of N-[2-(trimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0020]    quaternized propyl sulfate salt of N-[2-(dimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0021]    quaternized chloride salt of N-[2-(triethylamino)ethyl]-N′-[3-(diethylamino)-phenyl]urea;  
         [0022]    quaternized chloride salt of N-[2-(dimethylamino)ethyl]-N′-[3-(di-hydroxyethylamino)-phenyl]urea;  
         [0023]    quaternized methyl sulfate iodide salt of N-[2-(diethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea; and  
         [0024]    quaternized chloride salt of N-[2-(dimethylamino)ethyl]-N′-[3-(cyclohexylamino)-phenyl]urea.  
         [0025]    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.  
         [0026]    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,  
         [0027]    p-phenylenediamine derivatives such as: benzene-1,4-diamine (commonly known as p-phenylenediamine), 2-methyl-benzene-1,4-diamine, 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;  
         [0028]    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;  
         [0029]    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, and 2-amino-4-methyl-phenol; and  
         [0030]    heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonly known as 2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole-4,5-diamine, 2-(4,5-diamino-1 H-pyrazol-1-yl)ethanol, N 2 ,N 2 -dimethyl-pyridine-2,5-diamine, 2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol, 6-methoxy-N 2 -methyl-pyridine-2,3-diamine, 2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine, 1 -isopropyl-1 H-pyrazole-4,5-diamine, 1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, 1-(benzyl)-1H-pyrazole-4,5-diamine and 1-(4-chlorobenzyl)-1 H-pyrazole-4,5-diamine.  
         [0031]    The couplers of formula (1) of this invention may be used with any suitable coupler(s) in hair coloring compositions or systems of this invention.  
         [0032]    Suitable known couplers include, for example:  
         [0033]    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-methyl phenol, 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;  
         [0034]    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-mehyl-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-amino-4-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]-4,6-dimethoxyphenyl}-amino)ethanol, 3-(2,4-diaminophenoxy)-propane-1,2-diol, 2-[2-amino-4-(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-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine, and 2,4-dimethoxybenzene-1,3-diamine;  
         [0035]    m-aminophenols such as: 3-amino-phenol, 2-(3-hydroxy-4-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-amino-4-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  
         [0036]    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-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol, 1 H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1 H-indole-5,6-diol, 1 H-indol-7-ol, 1 H-indol-5-ol, 1 H-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, 1 H-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.  
         [0037]    Preferred primary intermediates include:  
         [0038]    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, and 1-(2,5-diaminophenyl)ethane-1,2-diol;  
         [0039]    p-aminophenol derivatives such as 4-amino-phenol, 4-methylamino-phenol, 4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol, and 1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;  
         [0040]    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;  
         [0041]    heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine, 1-methyl-1 H-pyrazole-4,5-diamine, 2-(4,5-diamino-1 H-pyrazol-1-yl)ethanol, 1-(4-methylbenzyl)-1 H-pyrazole-4,5-diamine, 1-(benzyl)-1 H-pyrazole-4,5-diamine and N 2 ,N 2 -dimethyl-pyridine-2,5-diamine.  
         [0042]    Preferred couplers include:  
         [0043]    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;  
         [0044]    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-amino-4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1-ol;  
         [0045]    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  
         [0046]    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, 1 H-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.  
         [0047]    Most preferred primary intermediates include:  
         [0048]    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, and 2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;  
         [0049]    p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino-phenol, 4-amino-3-methyl-phenol, and 1 -(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;  
         [0050]    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  
         [0051]    heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine, 2-(4,5-diamino-1 H-pyrazol-1 -yl)ethanol, 1 -(4-methylbenzyl)-1 H-pyrazole4,5-diamine, and 1 -(benzyl)-1 H-pyrazole-4,5-diamine.  
         [0052]    Most preferred couplers include:  
         [0053]    phenols, resorcinol and naphthol derivatives such as: benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol, and 2-methyl-benzene-1,3-diol;  
         [0054]    m-phenylenediamine such as: 2-(2,4-diamino-phenoxy)-ethanol, 2-(3-amino-4-methoxy-phenylamino)-ethanol, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and 3-(2,4-diamino-phenoxy)-propan-1 -ol;  
         [0055]    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  
         [0056]    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 H-indol-6-ol, and 2-aminopyridin-3-ol.  
         [0057]    Understandably, the coupler compounds and the primary intermediate compounds, as well as the other dye compounds, in so far as they are bases, can be used as free bases or in the form of their physiologically compatible salts with organic or inorganic acids, such as hydrochloric acid or sulfuric acid, or, in so far as they have aromatic OH groups, in the form of their salts with bases, such as alkali phenolates.  
         [0058]    The total amount of the combination of dye precursors (e.g., primary intermediate and coupler compounds) in the hair coloring compositions or systems of this invention is generally from about 0.001 to about 10, preferably from about 0.02 to about 10, and most preferably from about 0.2 to about 6.0 weight percent based on the total weight of the hair coloring composition. The primary intermediate and coupler compounds are generally used in equivalent amounts. However, it is possible to use the primary intermediate compounds in either excess or deficiency, i.e., a molar ratio of primary intermediate to coupler generally ranging from about 5:1 to about 1:5.  
         [0059]    The hair coloring compositions of this invention will contain the couplers of this invention in an effective coloring amount, generally in an amount of from about 0.001 to about 6 weight percent by weight of the hair dye composition, preferably from about 0.01 to about 3.5 weight percent. Other couplers, when present, are typically present in an amount such that in aggregate the concentration of couplers in the composition is from about 0.01 to about 6 weight percent. The primary intermediate(s) is present in an effective dyeing concentration generally an amount of from about 0.001 to about 6.0 weight percent by weight of the hair dye composition, preferably from about 0.01 to about 3.5 weight percent. Any suitable carrier or vehicle, generally an aqueous or hydroalcoholic solution, can be employed, preferably an aqueous solution. The carrier or vehicle will generally comprise up to about 40 weight percent.  
         [0060]    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.  
         [0061]    The compositions of the present invention are used by admixing them with a suitable oxidant, which reacts with the hair dye precursors to develop the hair dye. 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. Also suitable are urea peroxide, sodium perborate, sodium percarbonate, and melamine peroxide.  
         [0062]    Moreover, cosmetic additive ingredients, which are commonly used in compositions for coloring hair, can be used in the hair coloring compositions according to the invention, for example antioxidants, such as ascorbic acid, thioglycolic acid or sodium sulfite, and perfume oils, complex formers, wetting agents, emulsifiers, thickeners and care materials.  
         [0063]    The form of the hair coloring compositions according to the invention can be, for example, a solution, especially an aqueous or aqueous-alcoholic solution. However, the form that is particularly preferred is a cream, gel or an emulsion. Its composition is a mixture of the dye ingredients with the conventional cosmetic additive ingredients suitable for the particular preparation.  
         [0064]    Conventional cosmetic additive ingredients in solutions, creams, emulsion or gels include, for example:  
         [0065]    Solvents: In addition to water, solvents that can be used are lower alkanols (e.g.,ethanol, propanol, isopropanol); polyols (e.g., carbitols, propylene glycol, glycerin). Under suitable processing, higher alcohols, such as cetyl alcohol, are suitable organic solvents, provided they are first liquified by melting, typically at low temperature (50 to 80 deg. C.), before incorporation of other, usuually lipophilic, materials. See WO Ser. No. 98/27941 (section on diluents) incorporated by reference.  
         [0066]    Anionic and Nonionic Surfactants: These materials are from the classes of anionic, cationic, amphoteric or nonionic surfactant compounds, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzensulfonates, al kyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanol amides and ethoxylated fatty acid esters. They are included for various reasons, e.g., to assist in thickening, for forming emulsions, to help in wetting hair during application of the hair dye composition, etc. Suitable materials are alkyl sulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, acyl isethionates, alkyl ethoxy carboxylates, fatty acid monoand diethanolamides. Reference is made to WO Ser. No. 98/52523 published Nov. 26, 1998 and incorporated herein by reference.  
         [0067]    Thickeners: Suitable thickeners include such as higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oil, fatty acids and anionic and nonionic polymeric thickeners based on polyacrylic and polyurethane polymers. Examples are hydroxyethyl cellulose, hydroxymethylcellulose and other cellulose derivatives, hydrophobically modified anionic polymers and nonionic polymers, particularly such polymers having both hydrophilic and hydrophobic moieties (i.e., amphiphilic polymers). Useful nonionic polymers include polyurethane derivatives such as PEG-150/stearyl alcohol/SDMI copolymer and PEG-150/stearyl alcohol SDMI copolymer. Other useful amphiphilic polymers are disclosed in U.S. Pat. No. 6010541 incorporated by reference. Examples of anionic polymers that can be used as thickeners are acrylates copolymer, acrylates/ceteth-20 methacrylates copolymer, acrylates/ceteth-20 itaconate copolymer, and acrylates/beheneth-25 acrylates copolymer. Aculyn® polymers sold by Rohm &amp; Haas, as well as hair care materials, such as cationic resins, lanolin derivatives, cholesterol, pantothenic acids and betaine.  
         [0068]    Alkalizing agents: Suitable materials that are used to increase pH of the hair dye compositions include ammonia, aminomethylpropanol, methylethanolamine, triethanolamine and ethanolamine.  
         [0069]    Conditioners: Suitable materials include silicones and silicone derivatives; hydrocarbon oils; monomeric quaternary compounds, and quaternized polymers. Monomeric quaternary compounds are typically cationic compounds, but may also include betaines and other amphoteric and zwitterionic materials. Suitable monomeric quaternary compounds include behentrialkonium chloride, behentrimonium chloride, benzalkonium bromide or chloride, benzyl triethyl ammonium chloride, bis-hydroxyethyl tallowmonium chloride, C12-18 dialkyidimonium chloride, cetalkonium chloride, ceteartrimonium bromide and chloride, cetrimonium bromide, chloride and methosulfate, cetylpyridonium chloride, cocamidoproypi ethyidimonium ethosulfate, cocamidopropyl ethosulfate, coco-ethyldimonium ethosulfate, cocotrimonium chloride and ethosulfate, dibehenyl dimonium chloride, dicetyldimonium chloride, dicocodimonium chloride, dilauryl dimonium chloride, disoydimonium chloride, ditallowdimonium chloride, hydrogenated tallow trimonium chloride, hydroxyethyl cetyl dimonium chloride, myristalkonium chloride, olealkonium chloride, soyethomonium ethosulfate, soytrimonium chloride, stearalkonium chloride, and many other compounds. See WO Ser. No. 98/27941 incorporated by reference. Quaternized polymers are typically cationic polymers, but may also include amphoteric and zwitterionic polymers. Useful polymers are exemplified by polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-1 0, polyquaternium-22, polyquaternium-32, polyquaternium-39, polyquaternium-44 and polyquaternium-47. Silicones suitable to condition hair are dimethicone, amodimethicone, dimethicone copolyol and dimethiconol. See also WO Ser. No. 99/34770 published Jul. 15,1999, incorporated by reference, for suitable silicones. Suitable hydrocarbon oils would include mineral oil.  
         [0070]    Natural ingredients: For example, protein derivatives, aloe, camomile and henna extracts.  
         [0071]    Other adjuvants include acidulents to lower pH, buffers, chelating agents antioxidants, sequestrants, etc. These classes of materials and other species of materials in the classes referred to above but not specifically identified that are suitable are listed in the International Cosmetics Ingredient Dictionary and Handbook, (Eighth Edition) published by The Cosmetics, Toiletry, and Fragrance Association, incorporated by reference. In particular reference is made to Volume 2, Section 3 (Chemical Classes) and Section 4 (Functions) are useful in identifying a specific adjuvant/excipient to achieve a particular purpose or multipurpose.  
         [0072]    The above-mentioned conventional cosmetic ingredients are used in amounts suitable for their purposes. For example the wetting agents and emulsifiers are used in concentrations of from about 0.5 to 30 percent by weight, the thickeners are used in an amount of from about 0.1 to 25 percent by weight and the hair care materials are used in concentrations of from about 0.1 to 5.0 percent by weight.  
         [0073]    The hair coloring compositions according to the invention can be weakly acidic, neutral or alkaline according to their composition. The compositions typically have pH values of from 6.8 to 11.5. Their pH can be adjusted in the basic range with ammonia. Also, organic amines can be used for this purpose, including monoethanolamine and triethanolamine, or also inorganic bases, such as sodium hydroxide and potassium hydroxide. Inorganic or organic acids can be used for adjusting the pH in the acid range, for example phosphoric acid, acetic acid, citric acid or tartaric acid.  
         [0074]    In order to use the oxidation hair coloring composition for dyeing hair one mixes the above-described hair coloring compositions according to the invention with an oxidizing agent immediately prior to use and applies a sufficient amount of the mixture to the hair, according to the hair abundance, generally from about 60 to 200 grams. Some of the adjuvants listed above (e.g., thickeners, conditoners, etc.) can be provided in the dye composition or the developer, or both, depending on the nature of the ingredients, possible interactions, etc., as is well known in the art.  
         [0075]    Typically hydrogen peroxide, or its addition compounds with urea, melamine, sodium borate or sodium carbonate, can be used in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution as the oxidizing agent for developing the hair dye. Oxygen can also be used as the oxidizing agent. If a 6 percent hydrogen peroxide solution is used as oxidizing agent, the weight ratio of hair coloring composition and oxidizing agent is 5:1 to 1:2, but preferably 1:1. The mixture of the oxidizing agent and the dye composition of the invention is allowed to act on the hair for about 10 to about 45 minutes, preferably about 30 minutes, at about 15 to 50° C., the hair is rinsed with water and dried. If necessary, it is washed with a shampoo and eventually after-rinsed with a weak organic acid, such as citric acid or tartaric acid. Subsequently the hair is dried.  
         [0076]    The hair coloring composition according to the invention with a compound of formula (1) of this invention as coupler substances permits hair dyeing with outstanding color fastness, especially light fastness, fastness to washing and fastness to rubbing.  
         [0077]    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. Optionally, a separate conditioning product may also be provided. Together the hair dye composition of the present invention comprising the hair dye coupler (1) and the developer comprising the oxidizing agent form a system for dyeing hair. This system may be provided as a kit comprising in a single package separate containers of the hair dye compositions, the developer, the optional conditioner or the hair treatment product, and instructions for use.  
       EXAMPLE 11  
       [0078]    The following compositions shown in Table 1 can be used for dyeing Piedmont hair. The dyeing solution is mixed with 100 g 20 volume hydrogen peroxide. The resulting mixture is applied to the hair and permitted to remain in contact with the hair for 30 minutes. The dyed hair is then shampooed and rinsed with water and dried.  
                             TABLE 1                           Composition for Dyeing Hair            Ingredients   Range (wt %)   Weight (%)               Cocamidopropyl betaine   0-25   17.00        Monoethanolamine 1     0-15   2.00       Oleic Acid   2-22   0.75       Citric Acid   0-3    0.10       28% Ammonium hydroxide 1     0-15   5.00       Behentrimonium chloride   1-5    0.50       Sodium sulfite   0-1    0.10       EDTA   0-1    0.10       Erythorbic acid   0-1    0.40       Ethoxydiglycol   1-10   3.50       C11-15 Pareth-9 (Tergitol 15-S-9)   0.5-5     1.00       C12-15 Pareth-3 (Neodol 25-3)   0.25-5      0.50       Isopropanol   2-10   4.00       Propylene glycol   1-12   2.00       P-Phenylenediamine 2     0-5    2 mmoles       N,N-Bis(hydroxyethyl)-p-phenylene   0-5    2 mmoles       diamine 2         3-Methyl-p-aminophenol 2     0-5    1 mmoles       p-Aminophenol 2     0-5    5 mmoles       Coupler of this invention   0.5-5     5 mmoles       5-Amino-2-Methyl Phenol   0-5    2 mmoles       2,4-Diaminophenoxyethanol   0-5    2 mmoles       Water   qs to 100.00   qs to 100.00                                  
 
         [0079]    Exemplary combinations of hair coloring components employing a quaternizerd urea salt of formula (1) of this invention are shown in combinations OF Table 1 and in C1 to C126 in Table A. Reading down the columns in Table A, the Xes designate the dye compounds (including the novel couplers of the instant invention) that form illustratively suitable 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 quaternized urea salt of formula (1) of this invention, wherein R, R 1 , R 2 , R 4  and R 5  are as defined hereinbefore, can be combined with p-toluene diamine and 2-amino-phenol. Especially preferred as the quaternized urea salt of formula (1) are:  
         [0080]    quaternized iodide salt of N-[2-(trimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0081]    quaternized chloride salt of N-[2-(d imethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0082]    quaternized chloride salt of N-[2-(trimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0083]    quaternized bromide salt of N-[2-(triimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0084]    quaternized methyl sulfate salt of N-[2-(trimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0085]    quaternized propyl sulfate salt of N-[2-(dimethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea;  
         [0086]    quaternized chloride salt of N-[2-(triethylamino)ethyl]-N′-[3-(diethylamino)-phenyl]urea; quaternized chloride salt of N-[2-(dimethylamino)ethyl]-N′-[3-(di-hydroxyethylamino)-phenyl]urea;  
         [0087]    quaternized methyl sulfate iodide salt of N-[2-(diethylamino)ethyl]-N′-[3-(dimethylamino)-phenyl]urea; and  
         [0088]    quaternized chloride salt of N-[2-(dimethylamino)ethyl]-N′-[3-(cyclohexylamino)-phenyl]urea.  
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                     TABLE A                           DYE COMBINATIONS            Structure   IUPAC Name   Name   C1   C2   C3   C4   C5   C6   C7   C8   C9   C10                                             N-2-Trialkylaminoethyl- N′-3- dialkylaminophenyl- urea halide   N-2-Trialkylaminoethyl N′-3- dialkylaminophenyl urea halide   X   X   X   X   X   X   X   X   X   X                                             2-Methyl-benzene- 1,4-diamine   p-Toluene-diamine   X   X   X   X   X   X   X   X   X                                             Benzene-1,4-diamine   p-Phenylene-diamine                                       X                                             2-[(4-Amino-phenyl)- (2-hydroxy-ethyl)- amino]-ethanol   N,N-Bis(2- hydroxyethyl)-p- phenylene-diamine                                             4-Amino-phenol   p-Aminophenol                                             4-Amino-3-methyl- phenol   3-Methyl-p- aminophenol                                             2-Amino-phenol   o-Aminophenol   X                                   X                                             Benzene-1,3-diol   Resorcinol       X                                             2-Methyl-benzene- 1,3-diol   2-Methyl-resorcinol           X                                             Naphthalen-1-ol   1-Naphthol               X                                             2-Methyl-naphthalen- 1-ol   2-Methyl-1-naphthol                   X                                             2-(2,4-Diamino- phenoxy)-ethanol   2,4-Diamino- phenoxyethanol                       X                                             Benzene-1,3-diamine   m-Phenylenediamine                           X                                             3-Amino-phenol   m-Aminophenol                               X                                             5-Amino-2-methyl- phenol   2-Hydroxy-4- aminotoluene                                   X                                             2-(4,5-Diamino- pyrazol-1-yl)-ethanol   1-Hydroxyethyl-4,5- diamino-pyrazole                    DYE COMBINATIONS            Structure   C11   C12   C13   C14   C15   C16   C17   C18   C19   C20   C21   C22   C23   C24                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                                                             X   X   X   X   X   X                                             X   X   X   X   X   X   X   X                                                                                                                       X   X   X   X   X   X                                                                                                                       X                                             X                                   X                                                 X                                   X                                                     X                                   X                                                         X                                   X                                                             X                                   X                                                                 X                                                                     X                                                                         X                                                              DYE COMBINATIONS            Structure   C25   C26   C27   C28   C29   C30   C31   C32   C33   C34   C35   C36   C37   C38                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                             X   X   X                                       X   X                                                         X   X   X   X   X   X   X   X   X                                                                                             X   X                                             X   X   X   X   X   X   X   X   X   X   X   X                                                                                                   X                                   X                                                             X                                   X                                                                 X                                                                     X                                                                         X                                                                             X                                             X                                   X                                                 X                                   X                                                     X                                   X                                                              DYE COMBINATIONS            Structure   C39   C40   C41   C42   C43   C44   C45   C46   C47   C48   C49   C50   C51   C52                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                             X   X   X   X   X   X   X                                                                         X   X   X   X   X   X   X                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                                                                                                                                                 X                                                                                 X                                             X                                       X                                                 X                                       X                                                     X                                       X                                                         X                                       X                                                             X                                                                 X                                                                     X                                                              DYE COMBINATIONS            Structure   C53   C54   C55   C56   C57   C58   C59   C60   C61   C62   C63   C64   C65   C66                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                                                                           X   X                                             X   X                                                     x   X   X   X   X   X   X   X   X                                                                                         x   X   X                                                     x                                   x                                                         x                                   x                                                             x                                   x                                                                 x                                                                     x                                                                         x                                             X                               x                                                 X                               x                                                     X                               x                                                              DYE COMBINATIONS            Structure   C67   C68   C69   C70   C71   C72   C73   C74   C75   C76   C77   C78   C79   C80                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                                                                                                                                                                                                                         x   X   X   X   X   X   X   X                                                                     x   X   X   X   X   X   X   X                                             X   X   X   X   X   X                                                                     x                                                                         x                                                                             x                                             x                                   x                                                 x                                   x                                                     x                                   x                                                         x                                   x                                                             x                                   x                                                                 x                                                              DYE COMBINATIONS            Structure   C81   C82   C83   C84   C85   C86   C87   C88   C89   C90   C91   C92   C93   C94                                             X   X   X   X   X   X   X   X   X   X   X   X   X                                                                                     X   X   X   X                                                                                       X   X   X   X   X   X   X   X   X   X                                             X                                                 X   X   X   X   X   X   X   X   X                                                 X                                   X                                                     X                                   X                                                         X                                   X                                                             X                                   X                                                                 X                                                                     X                                                                         X                                                                             X                                             x                                   X                                                                                     X   X   X   X                    DYE COMBINATIONS            Structure   C95   C96   C97   C98   C99   C100   C101   C102   C103   C104   C105   C106   C107   C108                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                             X   X   X   X   X                                                                 X   X   X   X   X   X   X   X   X                                                                                                                                                                                                                                                                           X                                                                     X                                                                         X                                                                             X                                             X                                   X                                                 X                                   X                                                     X                                   X                                                         X                                   X                                                             X                                   X                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                    DYE COMBINATIONS            Structure   C109   C110   C111   C112   C113   C114   C115   C116   C117   C118   C119   C120   C121   C122                                             X   X   X   X   X   X   X   X   X   X   X   X   X   X                                                                                                                                                                           X   X   X   X   X   X   X   X   X                                                                                 X   X   X   X   X                                                                                 x                                                                                     x                                                                                         x                                                                                             x                                                                                                 x                                                                                                                                                                                                                     x   x   x   x   x   x   x   x   x   x   x   x   x   x                    DYE COMBINATIONS                Structure   C123   C124   C125   C126                                                     X   X   X   X                                                                                                                                                                                                                                                             X   X   X   x                                                                                                                                                                                                                                                                                                               x                                                         x                                                             x                                                                 x                                                     x   x   x   x                      
 
         [0089]    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.