TREA

Substituted 2-aminoalky-1,4-diaminobenzene compounds and oxidation dye precursor compositions containing same

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Information

  • Patent Grant
  • 6436152
  • Patent Number
    6,436,152
  • Date Filed
    Friday, October 20, 2000
    24 years ago
  • Date Issued
    Tuesday, August 20, 2002
    22 years ago
Information
Abstract
The oxidation hair dye precursor composition contains from 0.005 to 20.0 percent by weight of one or more coupler compounds and from 0.005 to 20.0 percent by weight of one or more developer compounds. The one or more developer compounds include at least one substituted 2-aminoalkyl-1,4-diaminobenzene compound of the formula (I): New substituted 2-aminoalkyl-1,4-diaminobenzene compounds of formula (I) are described.
Description




BACKGROUND OF THE INVENTION




1. Field of the Invention




The present invention relates to compositions for dyeing keratin fibers based on a developer-coupler substance combination, which contain at least one substituted 2-aminoalkyl-1,4-diaminobenzene compound as the developer substance. It also relates to new substituted 2-aminoalkyl-1,4-diaminobenzene compounds.




2. Prior Art




Oxidation dye precursor compounds have been important in the field of dyeing keratin fibers, especially hair, for a long time. The dye compounds for dyeing the keratin fibers are produced by reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent. The following compounds are examples of developer substances: 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, p-aminophenol and 1,4-diaminobenzene. The following compounds are examples of coupler substances: resorcinol, 4-chlororesorcinol, 1-naphthol, 3-aminophenol and derivatives of m-phenylenediamines.




There are numerous additional requirements of oxidation dye precursor compounds for dyeing human hair besides the resulting color in the desired intensity. The dye precursor compounds must be unobjectionable in toxicological and dermatological respects and the resulting hair color of the dyed hair must have good light fastness, permanent wave fastness, acid fastness and rubbing fastness. The color produced by dyeing the hair with the oxidation dye precursor compounds must remain stable in the presence of light, rubbing and chemical agents for at least four to six weeks. Moreover a broad palette of various color shades can be produced by combination of suitable developer and coupler substances.




The requirements for oxidation dye precursor compounds however cannot be completely fulfilled in every way with the currently known dye precursor compounds, as has been stated in the Monograph by K. H.Schrader, “Foundations and Formulations of Cosmetics [Grundlagen und Rezepturen der Kosmetika]”, 2nd Edition, pp. 784-799 (1989). There is therefore a need for new developer substances, which fulfill the above-described requirements to a special extent.




SUMMARY OF THE INVENTION




It is therefore an object of the present invention to provide improved developer compounds for use in a method of dyeing keratin fibers, especially human hair.




It is also an object of the present invention to provide new substituted 2-aminoalkyl-1,4-diaminobenzene compounds for use as developer substances in oxidation dye precursor compositions.




It has now been found surprisingly that certain substituted 2-aminoalkyl-1,4-diaminobenzene compounds of the general formula (I) fulfill the special requirements for developer substances to an especially great extent. When these developer substances are used together with most known coupler substances especially intense colors are produced, which are extraordinarily light-fast and wash-fast.




The new substituted 2-aminoalkyl-1,4-diaminobenzene compounds of the formula (I) according to the invention are:











wherein




R1, R2, R3 and R4, independently of each other, are each hydrogen, a C


1


- to C


6


-alkyl group, a C


1


- to C


4


-hydroxyalkyl group, a C


2


- to C


4


-dihydroxyalkyl group or a C


1


- to C


4


-alkoxy-(C


1


- to C


2


)alkyl group, or R1 and R2 or R3 and R4 together with the nitrogen atom form a four member to eight member aliphatic ring, and wherein at least two of the R1, R2, R3 and R4 substituent groups represent hydrogen;




R5 represents hydrogen, a halogen atom, a C


1


- to C


4


-alkyl group, a C


1


- to C


4


-hydroxyalkyl group or a C


1


- to C


4


-alkoxy group;




R6 and R7, independently of each other, each represent hydrogen, a C


1


- to C


2


-alkoxy group, a C


1


- to C


6


-alkyl group, a C


1


- to C


6


-alkenyl group, a C


1


- to C


4


-hydroxyalkyl group, a C


3


- to C


4


-dihydroxyalkyl group, a C


1


- to C


4


-aminoalkyl group, a C


1


- to C


4


-dimethylaminoalkyl group, a C


1


- to C


4


-acetylaminoalkyl group, a C


1


- to C


4


-methoxyalkyl group, a C


1


- to C


4


-ethoxyalkyl group, a C


1


- to C


4


-cyanoalkyl group, a C


1


- to C


4


-carboxyalkyl group, a C


1


- to C


4


-aminocarbonylalkyl group, a pyridylmethyl group, a furfuryl group, a hydrogenated furfuryl group, a substituted pyridyl group, a group of the formula II:











a group of the formula III:











a group of the formula IV:











wherein at least one of the R6 and R7 groups is not hydrogen, or R6 and R7 together with the nitrogen atom form one of the following rings:











R8 represents hydrogen or a C


1


- to C


6


-alkyl group;




R9 represents hydrogen, a carboxy group or an aminocarbonyl group;




R10 and R 11, independently of each other, each represent hydrogen, a hydroxy group, an aminocarbonyl group, a methylthiomethyl group, a substituted phenyl group having a phenyl group substituent or a hydroxy group substitutent or a group of the formula:











R12, R13, R14, R15 and R16 are each, independently of each other, hydrogen, a halogen atom, a cyano group, a hydroxy group, a C


1


- to C


4


-alkoxy group, a C


1


- to C


4


-hydroxyalkoxy group, a C


1


- to C


6


-alkyl group, a C


1


- to C


4


-alkylthioether group, a mercapto group, a nitro group, an amino group, an alkylamino group, a hydroxyalkylamino group, a dialkylamino group, a di(hydroxyalkyl)amino group, a (dihydroxyalkyl)amino group, a (hydroxyalkyl)alkylamino group, a trifluoromethane group, a —C(O)H group, a —C(O)CH


3


group, a —C(O)CF


3


group, a —Si(CH


3


)


3


group, a C


1


- to C


4


-hydroxyalkyl group, a C


3


- to C


4


-dihydoxyalkyl group, or two of the groups R12 to R16 next to each other form an —O—CH


2


—O— bridge;




R17 represents a C


1


- to C


4


-alkyl group or a a C


1


- to C


4


-hydroxyalkyl group; R18 represents hydrogen or a C


1


- to C


6


-alkyl group;




R19 represents one or more hydrogen, or hydroxy-, carboxy-, aminocarbonyl-, or hydroxymethyl group; and




R20 represents hydrogen or a C


1


- to C


6


-alkyl group, with the proviso that R


1


, R2 and R8 are not each hydrogen when (i) R3 and R4 are a C


1


- to C


4


-alkyl group or




R3 and R4 together with the nitrogen atom form a morpholino-, pyrrolidino-, piperidino- or hexamethylenimino ring, and when (ii) R5 is in the 5-position of the aromatic ring and R5 is hydrogen, a C


1


- to C


4


-alkyl group or a halogen atom, and




when (iii) R6 and R7, independently of each other, are a C


1


- to C


4


-alkyl group or a phenyl group or R3 and R4 taken together with the nitrogen atom form an unsubstituted piperidino- or pyrrolidino- ring;




or a physiologically compatible, water-soluble salt thereof.




The following are examples of the compounds of formula (I):




2-(2,3-dihydroxypropyl)aminomethyl-1,4-diaminobenzene; 2-ethylaminomethyl-1,4-diaminobenzene; 2-(isopropylaminomethyl)-1,4-diaminobenzene; 2-propylaminomethyl-1,4-diaminobenzene; 2-pyrrolidin-1-yl-methyl-1,4-diaminobenzene; 2-[(2-methoxyethylamino)methyl]-1,4-diaminobenzene; 2-morpholin-4-yl-methyl-1,4-diaminobenzene; 2-(2,5-diaminobenzylamino)-butan-1-ol; 2-{[(furan-2-ylmethyl)amino]methyl)-1,4-diaminobenzene; N-(2,5-diaminobenzyl)-O,N-dimethylhydroxylamine; 2-(4-methylpiperazin-1-yl-methyl)-1,4-diaminobenzene; 1-(2,5-diaminobenzyl)piperidin-4-ol; N-[2-(2,5-diaminobenzylamino)ethyl]acetamide; 2-[(2-morpholin-4-yl-ethylamino)methyl]-1,4-diaminobenzene; 2-allylaminomethyl-1,4-diaminobenzene; 2-(2,5-diaminobenzylamino)propan-1-ol; 2-[(3-imidazol-1-yl-propylamino)-methyl]-1,4-diaminobenzene; 2-{[(tetrahydrofuran-2-yl-methyl)amino]methyl}-1,4-diaminobenzene; 4-(2,5-diaminobenzylamino)aniline; 3-(2,5-diaminobenzylamino)phenol; 5-(2,5-diaminobenzylamino)-2-methylphenol; 2-[(2-dimethylaminoethylamino)-methyl]-1,4-diaminobenzene; 4-(2,5-diaminobenzylamino)butan-1-ol; 2-[(3-ethoxypropylamino)methyl]-1,4-diaminobenzene; 2-[(3-methoxy-phenylamino)-methyl]-1,4-diaminobenzene; 2-[(4-chlorophenylamino)methyl]-1,4-diaminobenzene; 2-[(cyclopropyl-methylamino)methyl]-1,4-diaminobenzene; 2-(2,5-diaminobenzylamino)-4-nitrophenol; 2-[(4-chlorobenzylamino)methyl]-1,4-diaminobenzene; 2-[(2,5-diaminobenzyl)methylamino]-ethanol; 2-[(2,5-diamino-benzyl)ethylamino]ethanol; 2{[(pyridin-4-yl-methyl)amino]methyl}-1,4-diaminobenzene; 1-[3-(2,5-diaminobenzylamino)-propyl]pyrrolidin-2-one; 2-(4-amino-2-methylphenyl)aminomethyl-1,4-diaminobenzene; 2-(4-amino-3-methylphenyl)aminomethyl-1,4-diaminobenzene; 2-[5-amino-2-(2,5-diamino-benzylamino)phenyl]ethanol; 2-(3-amino-phenyl)aminomethyl-1,4-diaminobenzene; 4-[2-(2,5-diaminobenzylamino)-ethyl]benzenesulfonamide; 2-[4-amino-2-(2,5-diaminobenzylamino)-phenoxy]ethanol; 2-[(2,5-diaminobenzyl)-(2-hydroxy-ethyl)amino]ethanol; [1-(2,5-diaminobenzyl)pyrrolidin-2-yl]-methanol; 1-(2,5-diaminobenzyl)pyrrolidin-3-ol; 1-(2,5-diaminobenzyl)-pyrrolidin-2-carboxylic acid amide; 1-(2,5-diaminobenzyl)-piperidin-3-ol; 2-(2,5-diamino-benzylamino)-propan-1,3-diol; 2-(2,5-diaminobenzylamino)-3-hydroxypropionamide; 2-(2,5-diaminobenzylamino)succinic acid; 2-cyclopropylaminomethyl-1,4-diaminobenzene; 2-(2,5-diaminobenzylamino)ethanol; (2,5-diaminobenzylamino)acetic acid; 4-(2,5-diaminobenzylamino)phenol; 2-(benzo[1,3]dioxol-5-yl-aminomethyl)-1,4-diaminobenzene; [(2,5-diaminobenzyl)-methyl-amino]acetonitrile; 2-pentyl-aminomethyl -1,4-diaminobenzene; 2-[(3-dimethylaminopropylamino)-methyl]-1,4-diaminobenzene; 2-{[2-(5-nitropyridin-2-yl-amino)ethylamino]-methyl}-1,4-diaminobenzene; 2-[(2-aminoethyl-amino)methyl]-1,4-diaminobenzene; 3-[2-(2,5-diaminobenzylamino)-1-hydroxyethyl]phenol; 2-[(4-methyl-pyridin-2-yl-amino)methyl]-1,4-diaminobenzene; 2-(2,5-diaminobenzyl)-1-methyl-1,2,3,4-tetrahydroisoquinolin-6,7-diol; 2-(2,5-diamino-benzylamino)-4-methylsulfanyl-butyric acid; 1-(2,5-diaminobenzyl)-pyrrolidin-2-carboxylic acid; 2-phenylamino-methyl -1,4-diaminobenzene; 2-(4-dimethylamino-phenylaminomethyl-1,4-diaminobenzene; 1-[3-(2,5-diaminobenzylamino)phenyl]ethanol; 1-[4-(2,5-diaminobenzylamino)-phenyl]ethanol; 1-[2-(2,5-diaminobenzylamino)-phenyl]ethanol; 2-[(3,4-dimethoxyphenylamino)methyl]-1,4-diaminobenzene; 2-[(3-fluoro-2-methoxyphenylamino)-methyl]-1,4-diaminobenzene; 4-chloro-2-(2,5-diaminobenzylamino)-phenol; 2-[(4-trifluoromethyl-phenylamino)-methyl]-1,4-diamino-benzene; 2-(p-tolylaminomethyl)-1,4-diaminobenzene; N


4


-dihydroxypropyl-2-(di(hydroxyethyl)aminomethyl)-1,4-diaminobenzene; N


4


-dihydroxypropyl-2-(hydroxyethylaminomethyl)-1,4-diaminobenzene; N


4


-dihydroxypropyl-2-(methylaminomethyl)-1,4-diaminobenzene; N


4


-hydroxyethyl-2-(di(hydroxyethyl)aminomethyl)-1,4-diaminobenzene; N


4


-hydroxyethyl-2-(hydroxyethylaminomethyl)-1,4-diaminobenzene; N


4


-hydroxyethyl-2-(methylaminomethyl)-1,4-diaminobenzene; N


4


,N


4


-bis-(hydroxyethyl)-2-(di(hydroxyethyl)aminomethyl)-1,4-diaminobenzene; N


4


,N


4


-bis-(hydroxyethyl)-2-(hydroxyethylaminomethyl)-1,4-diaminobenzene; N


4


, N


4


-bis-(hydroxyethyl)-2-(methylaminomethyl)-1,4-diaminobenzene; N


1


-dihydroxypropyl-2-(di(hydroxyethyl)-aminomethyl)-1,4-diaminobenzene; N


1


-dihydroxypropyl-2-(hydroxyethyl-aminomethyl)-1,4-diaminobenzene; N


1


-dihydroxypropyl-2-(methylaminomethyl)-1,4-diaminobenzene; N


1


-dihydroxyethyl-2-di(hydroxyethyl)aminomethyl)-1,4-diaminobenzene; N


1


-hydroxyethyl-2-(hydroxyethylaminomethyl)-1,4-diaminobenzene; N


1


-hydroxyethyl-2-(hydroxyethylaminomethyl)-1,4-diaminobenzene; N


1


,N


1


-bis-(hydroxyethyl)-2-(di(hydroxyethyl)aminomethyl)-1,4-diaminobenzene; N


1


N,N


1


-bis-(hydroxyethyl)-2-(hydroxyethylaminomethyl)-1,4-diaminobenzene; N


1


,N


1


-bis(hydroxyethyl)-2-(methylaminomethyl)-1,4-diaminobenzene; 2-((2-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyphenylamino)methyl)-1,4-diaminobenzene; 2-((2-dimethylaminophenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methylphenylamino)methyl)-1,4-diamino-benzene;2-((2-trifluoromethylphenylamino)methyl)-1,4-diaminobenzene; 2-((3-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-methylphenylamino)methyl)-1,4-diaminobenzene; 2-((3-trifluoromethylphenylamino)-methyl)-1,4-diaminobenzene; 2-((2-bromophenylamino)methyl)-1,4-diaminobenzene; 2-((2-cyanophenylamino)methyl)-1,4-diaminobenzene; 2-((2-fluorophenylamino)methyl)-1,4-diaminobenzene; 2-((2-methoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((2-nitrophenylamino)methyl)-1,4-diaminobenzene; 2-((3-bromophenylamino)methyl)-1,4-diaminobenzene; 2-((3-cyanophenylamino)methyl)-1,4-diaminobenzene; 2-((3-fluorophenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((3-nitrophenylamino)methyl)-1,4-diaminobenzene; 2-((4-bromophenylamino)-methyl)-1,4-diaminobenzene; 2-((4-cyanophenylamino)-methyl)-1,4-diaminobenzene; 2-((4-fluorophenylamino)methyl)-1,4-diaminobenzene; 2-((4-methoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((4-nitrophenylamino)methyl)-1,4-diaminobenzene; 2-((2-(1,3-dihydroxypropyl)aminophenylamino)-methyl)-1,4-diaminobenzene; 2-((2-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-pyrrolidin-phenylamino)methyl)-1,4-diaminobenzene; 2-((3-( 1,3-dihydroxypropyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-pyrrolidin-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-(1,3-dihydroxypropyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-pyrrolidin-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-amino-2-(2-hydroxyethoxy)-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-amino-2-chlorophenylamino)-methyl)-1,4-diaminobenzene; 2-((4-amino-2-hydroxyphenylamino)methyl)-1,4-diaminobenzene; 2-((4-amino-2-methoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((4-amino-3-(2-hydroxyethoxy)phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-amino-3-chlorophenylamino)methyl)-1,4-diaminobenzene; 2-((4-amino-3-hydroxyphenylamino)methyl)-1,4-diaminobenzene; 2-((4-amino-3-methoxyphenylamino)-methyl)-1,4-diaminobenzene; 2-((3,4-diamino-phenylamino)methyl)-1,4-diaminobenzene; 2-((2,4-diaminophenylamino)methyl)-1,4-diaminobenzene; N


4


-dihydroxypropyl-2-((4-aminophenylamino)methyl)-1,4-diaminobenzene; N


4


-dihydroxypropyl-2-(phenylaminomethyl)-1,4-diaminobenzene; N


4


-dihydroxypropyl-2-((4-di(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene; N


4


-dihydroxypropyl-2-((4-hydroxyethylaminophenylamino)-methyl)-1,4-diaminobenzene; N


4


-hydroxyethyl-2-((4-aminophenylamino)methyl)-1,4-diaminobenzene; N


4


-hydroxyethyl-2-(phenylaminomethyl)-1,4-diaminobenzene; N


4


-hydroxyethyl-2-((4-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; N


4


-hydroxyethyl-2-((4-hydroxyethylaminophenylamino)-methyl)-1,4-diaminobenzene; N


4


,N


4


-bis-(hydroxyethyl)-2-(4-aminophenylamino)-methyl)-1,4-diaminobenzene; N


4


,N


4


-bis-(hydroxyethyl)-2-phenylaminomethyl)-1,4-diaminobenzene; N


4


,N


4


-bis-(hydroxyethyl)-2-(4-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; N


4


,N


4


-bis-(hydroxyethyl)-2-(4-hydroxyethylamino-phenylamino)methyl)-1,4-diaminobenzene; N


1


-dihydroxypropyl-2-((4-amino-phenylamino)methyl)-1,4-diaminobenzene; N


1


-dihydroxypropyl-2-(phenylaminomethyl)-1,4-diaminobenzene; N


1


-dihydroxypropyl-2-((4-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; N


1


-dihydroxypropyl-2-((4-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; N


1


-hydroxyethyl-2-((4-aminophenylamino)methyl)-1,4-diaminobenzene; N


1


-hydroxyethyl-2-(phenylaminomethyl)-1,4-diaminobenzene; N


1


-hydroxyethyl-2-((4-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; N


1


-hydroxyethyl-2-((4-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; N


1


, N


1


-bis-(hydroxyethyl)-2-(4-aminophenylamino)methyl)-1,4-diaminobenzene; N


1


, N


1


-bis-(hydroxyethyl)-2-phenylaminomethyl)-1,4-diaminobenzene; N


1


,N


1


-bis-(hydroxyethyl)-2-(4-di(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; N


1


,N


1


-bis-(hydroxyethyl)-2-(4-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-[5-amino-4-(2,5-diaminophenylamino)-pyrazol-1-yl]ethanol; N


2


-(5-amino-1-methyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene; N


2


-(5-amino-1-isopropyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene and N


2


-(5-amino-1,3-dimethyl-1H-pyrazol4-yl)-1,2,4-triaminobenzene.




The preferred compounds of formula (I) are those compounds, in which (i) one or more groups R5 and R8 are hydrogen and/or (ii) R1, R2, R3 and R4 simultaneously represent hydrogen and/or (iii) R6 represents a methyl group or a C


1


-C


4


-hydroxyalkyl group and R7 represents a C


1


-C


4


-hydroxyalkyl group and/or (iv) R6 represents hydrogen and R7 represents a C


1


-C


4


-hydroxyalkyl group, a substituted pyridyl group, a substituted phenyl group, a substituted pyrazoyl group or a group of the following formula:











and/or (v) R6 and R7 represent an aliphatic ring of the formula:











Particularly the following compounds are preferred examples of the compounds of formula (I): 2-(2,3-dihydroxypropyl)aminomethyl-1,4-diaminobenzene; 2-[(2-aminoethylamino)methyl]-1,4-diaminobenzene; 2-[(2-hydroxyethylamino)methyl]-1,4-diaminobenzene; 2-[(2,5-diaminobenzyl)methylamino]-ethanol; 2-(2,5-diaminobenzylamino)-propan-1-ol; 2-[(2,5-diaminobenzyl)-(2-hydroxyethyl)amino]ethanol; [1-(2,5-diaminobenzyl)pyrrolidin-2-yl]methanol; 1-(2,5-diaminobenzyl)-pyrrolidin-2-carbamide; 2-[(4-methylpyridin-2-yl-amino)methyl]-1,4-diaminobenzene; 2-((2-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-chlorophenylamino)methyl)-1,4-diaminobenzene; 2-((2-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-fluorophenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-N,N-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-pyrrolidinphenylamino)methyl)-1,4-diaminobenzene; 2-((3-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-chlorophenylamino)methyl)-1,4-diaminobenzene; 2-((3-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-fluorophenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-N,N-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-pyrrolidin-phenylamino)methyl)-1,4-diaminobenzene;2-((4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-chlorophenylamino)methyl)-1,4-diaminobenzene; 2-((4-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-fluorophenylamino)methyl)-1,4-diaminobenzene; 2-((4-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-N,N-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-pyrrolidinphenylamino)methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxy)-ethoxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-amino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-chloro-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyethylamino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-methyl-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxy)-ethoxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-amino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-chloro-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxyethylamino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-methyl-4-aminophenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxy)ethoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyphenylamino)methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxy)ethoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxyphenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxy)-ethoxy-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-hydroxyphenylamino)methyl)-1,4-diaminobenzene; 2-(phenylamino)methyl-1,4-diaminobenzene; 2-[5-amino-4-(2,5-diaminophenylamino)-pyrazol-1-yl]ethanol; N


2


-(5-amino-1-methyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene; N


2


-(5-amino-1-isopropyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene and N


2


-(5-amino-1,3-dimethyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene.




The compounds of formula I can be employed both as free bases and also in the form of their physiologically compatible salts with inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.




The method of making the substituted diaminobenzene derivatives according to formula (I) can occur using known synthetic methods. The synthesis of the compounds according to the invention, for example, can occur by the following methods: Either (a) by performing a reductive amination of a substituted benzene of formula (V)











in which Ra has the significance of a protective group, for example as described in the chapter, “Protective Groups” in Organic Synthesis, Chapter 7, Wiley Interscience, 1991; Rb represents NR1Ra or NR1R2; by reacting the compound of formula (V) with an amine of formula HNR6R7, wherein R1, R2, R5, R6, R7 and R8 have the same significance as in formula (I) above and subsequently splitting off the protective group; or




(b) by substitution of a substituted benzene of formula (VI)











with an amine of formula HNR1R2, reduction of the nitrile group, subsequent alkylation of the amino group with a compound of formula XR6 and/or XR7, and finally reduction of the nitro group, wherein R1, R2, R5, R6 and R7 have the same significance as in the above formula (I) and X represents a halogen atom.




The substituted 2-aminoalkyl-1,4-diaminobenzene compounds according to formula (I) are soluble in water and produce colors with a higher intensity and better fastness, especially light-fastness, wash-fastness and rubbing-fastness, than prior art developer compounds. The substituted 2-aminoalkyl-1,4-diaminobenzene compounds according to formula (I) have outstanding storage stability, especially as components of a subsequently described oxidation dye precursor composition.




The subject matter of the present invention also includes a composition for oxidative dyeing of keratin fibers, for example hairs, fur, fibers or wool, especially human hair, comprising a combination of coupler substance and developer substances, which contain at least one substituted 2-aminoalkyl-1,4-diaminobenzene compound of formula (I).




The at least one 2-aminoalkyl-1,4-diaminobenzene derivative compound of formula (I) is present in the oxidation dye precursor composition according to the invention in an amount of about 0.005 to 20 percent by weight, however an amount of about 0.01 to 8.0 percent by weight is preferred and 0.1 to 5.0 percent by weight is particularly preferred.




The coupler substance preferably can be 2,6-diamino-pyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)-amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene, 2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-diaminophenoxyacetic acid, 3-[(di(2-hydroxyethyl)-amino]-aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline, 3-[(2-amino-ethyl)-amino]aniline, 1,3-di(2,4-diaminophenoxy)propane, di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis(2-hydroxyethyl)aminotoluene, 4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dicholorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2-{(3-hydroxyphenyl)amino]-acetamide, 5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)-aminophenol, 3-[(2-methoxyethyl)amino]phenol, 5-amino-2-ethylphenol, 2-(4-amino-2-hydroxyphenoxy)ethanol, 5-[(3-hydroxypropyl)amino]-2-methylphenol, 3-[(2,3-dihydroxypropyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)amino]-2-methyl-phenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro-2-methyl-phenol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxy-naphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate, 1,3-dihydoxybenzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5-[(2-hydroxy-ethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxyindoline, 5-hydroxyindole, 6-hydroxy-indole, 7-hydroxyindole and 2,3-indolindione.




Although the advantageous properties of the above-described substituted 2-aminoalkyl-1,4-diaminobenzene compounds of formula (I) can obviously be obtained when the diaminobenzene derivative compounds of formula (I) are used alone, it is understandably also possible to use the 2-aminoalkyl-1,4-diaminobenzene compounds of formula (I) together with known developer substances, such as 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminophenyl-ethyl alcohol, 4-aminophenol and its derivatives, especially 4-amino-3-methylphenol, 4,5-diamino-1-(2-hydroxyethyl)pyrazole or tetraaminopyrimidines.




The coupler and developer substances can be contained in the oxidation dye precursor compositions according to the invention individually, or in mixtures with each other. The coupler substances and developer substances are contained in the dye precursor composition according to the invention (relative to the total amount of the dye precursor composition) in an amount of from about 0.005 to 20 percent by weight respectively. However an amount of from about 0.01 to 5.0 percent by weight is preferable and from 0.1 to 2.5 percent by weight is especially preferably.




The total amount of the combination of developer and coupler substances in the oxidation dye precursor composition described here is preferably from about 0.01 to 20 percent by weight, especially preferably from about 0.02 to 10 percent by weight, and most preferably from 0.2 to 6.0 percent by weight. The developer and coupler substances are used generally in equimolar amounts, however it is not disadvantageous when the developer substances are present in a certain excess or deficiency.




The dye compositions according to the invention can also contain certain other dye ingredients, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, as well as conventional direct-dyeing dye compounds, such as triphenylmethane dye compounds, such as 4-[(4′-aminophenyl)-(4′-imino-2″,5″-cyclohexadien-1″-yliden)-methyl]-2-methylaminobenzene monohydrochloride (C.I. 42 510) and 4-[(4′-amino-3′-methylphenyl)-(4″-imino-2″,5″-cyclohexadien-1″-yliden)methyl]-2-methylaminobenzene monohydrochloride (C.I. 42 520); aromatic nitro dye compounds, such as 4-(2′-hydroxyethyl)aminonitrotoluene, 2-amino-4,6-dinitrophenol, 2-amino-5-(2′-hydroxyethyl)aminonitrobenzene, 2-chloro-6-(ethylamino)-4-nitrophenol, 4-chloro-N-(2-hydroxyethyl)-2-nitroaniline, 5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitro-phenol and 1-[(2′-ureidoethyl)amino-4-nitrobenzene; azo dye compounds, such as 6-[(4′-aminophenyl)azo]-5-hydroxy-napththalen-1-sulfonic acid sodium salt (C.I. 14 805) and dispersion dye compounds, such as 1,4-diaminoanthraquinone and 1,4,5,8-tetraaminoanthraquinone. These additional dye compounds can be contained in the oxidation dye precurosr composition of the invention in an amount of from about 0.1 to 4.0 percent by weight.




Understandably the coupler substances and the developer substances as well as the other dye compounds, in so far as they are bases, can also be used 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.




Moreover cosmetic additive ingredients, which are commonly used in compositions for dyeing hair, can be used in the oxidation dye precursor 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. The form of the dye 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.




Conventional cosmetic additive ingredients in solutions, creams, emulsion or gels include, for example, solvents, such as water, lower aliphatic alcohols, such as ethanol, propanol or isopropanol, glycerol or glycols, such as 1,2-propylene glycol, wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surfactant compounds, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, aklylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanol amides and ethoxylated fatty acid esters; thickeners, such as higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oil and fatty acids, as well as care materials, such as cationic resins, lanolin derivatives, cholesterol, pantothenic acids and betaine. 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 care materials are used in concentrations of from about 0.1 to 5.0 percent by weight.




The oxidation dye precursor compositions according to the invention can be weakly acidic, neutral or alkaline according to their composition. These compositions preferably 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.




In order to use the oxidation hair dye precursor composition for dyeing hair one mixes the above-described compositions according to the invention with an oxidizing agent immediately prior to use and applies a sufficient amount of the ready-to-apply mixture to the hair, according to the hair abundance, generally from about 60 to 200 grams.




Principally 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. Air 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 dye composition and oxidizing agent is 5:1 to 1:2, but preferably 1:1. Larger amounts of oxidizing agent are used above all with larger dye concentrations in the oxidation dye precursor composition, or when at the same time a strong bleaching of the hair is desired. The mixture of the oxidizing agent and the oxidation dye precursor composition of the invention is allowed to act on the hair for about 10 to 45 minutes, preferably 30 minutes, at 15 to 65 degrees Celsius, 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.




The oxidation hair dye precursor compositions according to the invention with a content of the substituted 2-aminoalkyl-1,4-diaminobenzene compounds of formula (I) as developer substances permit hair dyeing with outstanding color fastness, especially light fastness, fastness to washing and fastness to rubbing. The dye precursor compositions according to the invention provide a broad palette of different color shades, which extend from blond to brown, purple, violet to blue and black shades, according to the type and composition of the dye compounds in it. Particularly the color shades produced have outstanding color intensity. The very good dyeing properties of the compositions according to the invention include the production of good color coverage and dyeing of gray, chemically not-previously damaged hair without problems.




The following examples should serve to illustrate the invention, but details present in these examples should not be considered as further limiting the following appended claims, unless they are explicitly included in the following appended claims.











EXAMPLES




Example 1




Synthesis of 2-(aminomethyl)-1,4-diaminobenzene Compounds (General Synthetic Recipe)




A. Synthesis of 2,5-bis.-tert.-butyloxycarbonylaminobromobenzene




15.65 g (0.07 mol)bromo-p-phenylenediamine hydrochloride and 32.7 g (0.15 mol)di-tert.-butyl-dicarbonate are dissolved in a mixture of 250 ml 2N sodium hydroxide and 250 ml trifluorotoluene and heated at 45° C. This reaction mixture is stirred for 3 days. Then 30 g (0.14 mol) di-tert.-butyl dicarbonate are gradually added. Subsequently the organic layer is separated and the aqueous phase is extracted twice with 100 ml dichloromethane. The combined extracts are evaporated to dryness and the residue is taken up in 200 ml of hexane. The precipitate is filtered and washed with 50 ml hexane. 18.6 g (82% of theoretical) of 2,5-bis-tert.-butyloxycarbonylaminobromobenzene is obtained with a melting point of 130° C.




B. Synthesis of N-(4-tert.-butyloxycarbonylamino-2-formylphenyl)carbamic acid-tert. butylester




3.3 g (0.01 mol) 2,5-bis-tert.-butyloxycarbonylaminobromobenzene from step A are dissolved in 100 ml of water-free tetrahydrofuran under argon. 17 ml of a 1.6 molar etheric methyl lithium solution (0.03 mol) are gradually added. The reaction mixture is cooled to −20° C., 7 ml of a 1.5 molar tert.-butyl lithium solution (0.01 mol) are gradually added. After the addition has ended the solution is stirred for 30 minutes at the given temperature. Subsequently 1.2 g of dimethyl formamide (0.02 mol) are added and the reaction mixture is stirred for one hour at −20° C. After slowly heating to room temperature the reaction mixture is hydrolyzed with water and then poured into ether, the aqueous phase is extracted with ether and then the organic phase is dried over magnesium sulfate. The solvent is distilled away in a rotary evaporator and the residue is purified on silica gel with a petroleum ether/ethyl acetate solvent (9/1).




C. Synthesis of Substituted 2-aminomethyl-1,4-diaminobenzene Compounds




0.033 g (0.0001 mol) N-(4-tert.-butyloxycarbonylamino-2-formylphenyl)-carbamic acid-tert.-butyl ester from step B and 0.00015 mol of the corresponding amines are dissolved in 1,2-dichloroethane. Subsequently 0.1 ml of an acetic acid solution (1M in 1,2-dichloroethane) and 0.06 g NaBH(OAc)


3


(0.0003 mol) are added and the reaction mixture is stirred from 5 to 15 hours at room temperature.




After ending the reaction the reaction mixture is poured into 10 ml of ethyl acetate, the organic phase is extracted with sodium hydrogen carbonate and then dried with magnesium sulfate. The solvent is distilled off in a rotary evaporator and the residue is purified with petroleum ether/ethyl acetate (9:1). The product thus obtained is heated in 4 ml ethanol at 50° C.




Subsequently 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution are added drop-wise. The precipitate is filtered off, washed twice with 1 ml ethanol and then dried.




a1. 2-ethylamino-1,4-diaminobenzene hydrochloride




Amine Used: ethylamine




Yield: 0.025 g (91% of theory)




Mass Spectrum MH


+


166(100)




b1. 2-(isopropylaminomethyl)-1,4-diaminobenzene hydrochloride




Amine Used: isopropylamine




Yield: 0.017 g (59% of theory)




Mass Spectrum MH


+


180(100)




c1. 2-propylaminomethyl-1,4-diaminobenzene hydrochloride




Amine Used: propylamine




Yield: 0.025 g (87% of theory)




Mass Spectrum MH


+


180(100)




d1. 2-pyrrolidin-1-ylmethyl-1,4-diaminobenzene hydrochloride




Amine Used: pyrrolidine




Yield: 0.025 g (83% of theory)




Mass Spectrum MH


+


192(100)




e1. 2-[(2-methoxyethylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 2-methoxyethylamine




Yield: 0.025 g (82% of theory)




Mass Spectrum MH


+


196(100)




f1. 2-morpholin-4-ylmethyl-1,4-diaminobenzene hydrochloride




Amine Used: morpholine




Yield: 0.0259 (79% of theory)




Mass Spectrum MH


+


208(100)




g1. 2-(2,5-diaminobenzylamino)butan-1-ol hydrochloride




Amine Used: 2-amino-1-butanol




Yield: 0.025 g (78% of theory)




Mass Spectrum MH


+


210(100)




h1. 2-{[(furan-2-ylmethyl)amino]methyl}-1,4-diaminobenzene hydrochloride




Amine Used: furfurylamine




Yield: 0.025 g (76% of theory)




Mass Spectrum MH


+


218(100)




i1. N-(2,5-diaminobenzyl)-O,N-dimethylhydroxylamine hydrochloride




Amine Used: O, N-dimethylhydroxylamine




Yield: 0.025 g (86% of theory)




Mass Spectrum MH


+


182(100)




j1. 2-(4-methylpiperazin-1-ylmethyl)-1,4-diaminobenzene hydrochloride




Amine Used: 4-methylpiperazine




Yield: 0.025 g (68% of theory)




Mass Spectrum MH


+


221 (100)




k1. 1-(2,5-diaminobenzyl)piperidin-4-ol hydrochloride




Amine Used: 4-hydroxypiperidine




Yield: 0.025 g (76% of theory)




Mass Spectrum MH


+


222(100)




l1. N-[2-(2,5-diaminobenzylamino)ethyl]acetamide hydrochloride N-acetylethylenediamine




Amine Used: ethylamine




Yield: 0.025 g (75% of theory)




Mass Spectrum MH


+


223(100)




m1. 2-[(2-morpholin-4-yl-ethylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 4-(2-ethylamino)morpholine




Yield: 0.025 g (63% of theory)




Mass Spectrum MH


+


251 (100)




n1. 2-allylaminomethyl-1,4-diaminobenzene hydrochloride




Amine Used: allylamine




Yield: 0.025 g (87% of theory)




Mass Spectrum MH


+


178(100)




o1. 2-(2,5-diaminobenzylamino)propan-1-ol hydrochloride




Amine Used: 2-aminopropanol




Yield: 0.025 g (82% of theory)




Mass Spectrum MH


+


196(100)




p1. 2-[(3-imidazol-1-ylpropylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 1-(3-aminopropyl)imidazole




Yield: 0.025 g (64% of theory)




Mass Spectrum MH


+


246(100)




q1. 2-{[(tetrahydrofuran-2-ylmethyl)amino]methyl}-1,4-diaminobenzene hydrochloride




Amine Used: tetrahydrofurfurylamine




Yield: 0.025 g (76% of theory)




Mass Spectrum MH


+


222(100)




r1. 4-(2,5-diaminobenzylamino)aniline hydrochloride




Amine Used: 4-tert.-butyloxycarbonylaminoaniline




Yield: 0.025 g (67% of theory)




Mass Spectrum MH


+


229(100)




s1. 3-(2,5-diaminobenzylamino)phenol hydrochloride




Amine Used: 3-aminophenol




Yield: 0.025 g (74% of theory)




Mass Spectrum MH


+


230(100)




t1. 5-(2,5-diaminobenzylamino)-2-methylphenol hydrochloride




Amine Used: 3-amino-6-methylphenol




Yield: 0.025 g (71% of theory)




Mass Spectrum MH


+


244(100)




u1. 2-[(2-dimethylaminoethylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 2-dimethylaminoethylamine




Yield: 0.016 g (45% of theory)




Mass Spectrum MH


+


209(100)




v1. 4-(2,5-diaminobenzylamino)butan-1-ol hydrochloride




Amine Used: 4-aminobutanol




Yield: 0.022 g (69% of theory)




Mass Spectrum MH


+


210(100)




w1. 2-[(3-ethoxypropylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 3-ethoxypropylamine




Yield: 0.025 g (75% of theory)




Mass Spectrum MH


+


224(100)




x1. 2-[(3-methoxyphenylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 3-methoxyaniline




Yield: 0.025 g (71% of theory)




Mass Spectrum MH


+


244(100)




y1. 2-[(4-chlorophenylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 4-chloroaniline




Yield: 0.025 g (70% of theory)




Mass Spectrum MH


+


248(100)




z1. 2-[(cyclopropylmethylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: aminomethylcyclopropane




Yield: 0.01 7 g (56% of theory)




Mass Spectrum MH


+


192(100)




a2. 2-(2 5-diaminobenzylamino)-4-nitrophenol hydrochloride




Amine Used: 2-amino-4-nitrophenol




Yield: 0.025 g (65% of theory)




Mass Spectrum MH


+


275(100)




b2. 2-[(4-chlorobenzylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 4-chlorobenzylamine




Yield: 0.025 g (67% of theory)




Mass Spectrum MH


+


262(100)




c2. 2-[(2,5-diaminobenzyl)methylamino]ethanol hydrochloride




Amine Used: 2-methylaminoethanol




Yield: 0.025 g (82% of theory)




Mass Spectrum MH


+


196(100)




d2. 2-[(2,5-diaminobenzyl)ethylamino]ethanol hydrochloride




Amine Used: 2-ethylaminoethanol




Yield: 0.025 g (78% of theory)




Mass Spectrum MH


+


210(100)




e2. 2-{[(pyridin-4-ylmethyl)amino]methyl}-1,4-diaminobenzene hydrochloride




Amine Used: 4-picolylamine




Yield: 0.025 g (67% of theory)




Mass Spectrum MH


+


229(100)




f2. 1-[3-(2,5-diaminobenzylamino)propyl]pyrrolidin-2-one hydrochloride




Amine Used: 1-(3-aminopropyl)-2-pyrrolidone




Yield: 0.025 g (67% of theory)




Mass Spectrum MH


+


263(100)




g2. 2-(4-amino-2-methylphenyl)aminomethyl-1,4-diaminobenzene hydrochloride and 2-(4-amino-3-methylphenyl)aminomethyl-1,4-diaminobenzene hydrochloride




Amines Used: 4-tert.-butyloxycarbonylamino-3-methylaniline and 4 tert.-butyloxycarbonylamino-2-methylaniline




Yield: 0.021 g (27% of theory)




Mass Spectrum MH


+


243(100)




h2. 2-[5-amino-2-(2,5-diaminobenzylamino)phenyl]ethanol hydrochloride and 2-[2-amino-5-(2,5-diaminobenzylamino)phenyl]ethanol hydrochloride




Amines Used: 4-tert.-butyloxycarbonylamino-3-(2-hydroxyethyl)aniline and 4 tert.-butyloxycarbonylamino-2-(2-hydroxyethyl)aniline




Yield: 0.025 g (30% of theory)




Mass Spectrum MH


+


273(100)




i2. 2-(3-aminophenyl)aminomethyl-1,4-diaminobenzene hydrochloride




Amine Used: 3-tert.-butyloxycarbonylaminoaniline




Yield: 0.025 g (67% of theory)




Mass Spectrum MH


+


229(100)




j2. 4-[2-(2,5-diaminobenzylamino)ethyl]benzene sulfonamide hydrochloride




Amine Used: 4-(2-aminoethyl)benzene sulfonamide




Yield: 0.025 g (58% of theory)




Mass Spectrum MH


+


321(100)




k2. 2-[4-amino-2-(2 5-diaminobenzylamino)phenoxy]ethanol hydrochloride




Amine Used: 4-tert.-butyloxycarbonylamino-2-amino-(2-hydroxy)ethoxybenzene




Yield: 0.025 g (58% of theory)




Mass Spectrum MH


+


289(100)




l2. 2-[(2,5-diaminobenzyl)-(2-hydroxyethyl)amino]ethanol hydrochloride




Amine Used: diethanolamine




Yield: 0.0259 (75% of theory)




Mass Spectrum MH


+


226(100)




m2. [1-(2,5-diaminobenzyl)pyrrolidin-2-yl]methanol hydrochloride




Amine Used: prolinol




Yield: 0.025 g (76% of theory)




Mass Spectrum MH


+


222(100)




n2. 1-(2,5-diaminobenzyl)pyrrolidin-3-ol hydrochloride




Amine Used: 3-hydroxypyrrolidine




Yield: 0.025 g (79% of theory)




Mass Spectrum MH


+


208(100)




o2. 1-(2,5-diaminobenzyl)pyrrolidin-2-carboxamide hydrochloride




Amine Used: prolinamide




Yield: 0.025 g (73% of theory)




Mass Spectrum MH


+


235(100)




p2. 1-(2,5-diaminobenzyl)piperdin-3-ol hydrochloride




Amine Used: 3-hydroxypiperidine




Yield: 0.025 g (76% of theory)




Mass Spectrum MH


+


222(100)




q2. 2-(2,5-diaminobenzylamino)propan-1,3-diol hydrochloride




Amine Used: 3-amino-12-propandiol




Yield: 0.015 g (47% of theory)




Mass Spectrum MH


+


212(100)




r2. 2-(2,5-diaminobenzylamino)-3-hydroxypropionamide hydrochloride




Amine Used: 3-hydroxy-2-aminopropionamide




Yield: 0.025 g (75% of theory)




Mass Spectrum MH


+


225(100)




s2. 2-(2,5-diaminobenzylamino)-succinic acid hydrochloride




Amine Used: aspargine




Yield: 0.037 g (102% of theory)




Mass Spectrum MH


+


253 (100)




t2. 2-cyclopropylaminomethyl-1,4-diaminobenzene hydrochloride




Amine Used: cyclopropylamine




Yield: 0.025 g (87% of theory)




Mass Spectrum MH


+


178(100)




u2. 2-(2 5-diaminobenzylamino)ethanol hydrochloride




Amine Used: ethanolamine




Yield: 0.025 g (86% of theory)




Mass Spectrum MH


+


182(100)




v2. (2,5-diaminobenzylamino)acetic acid hydrochloride




Amine Used: glycine




Yield: 0.025 g (82% of theory)




w2. 4-(2,5-diaminobenzylamino)phenol hydrochloride




Amine Used: 4-aminophenol




Yield: 0.025 g (75% of theory)




Mass Spectrum MH


+


230(100)




x2. 2-(benzo[1,3]dioxol-5-ylaminomethyl)-1,4-diaminobenzene hydrochloride




Amine Used: 3,4-methylenedioxyaniline




Yield: 0.025 g (68% of theory)




Mass Spectrum MH


+


258(100)




y2. [(2,5-diaminobenzyl)methylamino)acetonitrile hydrochloride




Amine Used: methylaminoacetonitrile




Yield: 0.025 g (83% of theory)




Mass Spectrum MH


+


191 (100)




z2. 2-pentylaminomethyl-1,4-diaminobenzene hydrochloride




Amine Used: pentylamine




Yield: 0.025 g (79% of theory)




Mass Spectrum MH


+


208(100)




a3. 2-[(3-dimethylaminopropylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 3-dimethylaminopropylamine




Yield: 0.025 g (68% of theory)




Mass Spectrum MH


+


223(100)




b3. 2-[2-(5-nitropyridin-2-ylamino)ethylaminolmethyl]-1,4-diaminobenzene hydrochloride




Amine Used: 2-amino-5-nitropyridine




Yield: 0.025 g (56% of theory)




Mass Spectrum MH


+


303(100)




c3. 2-[(2-aminoethylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: ethylenediamine




Yield: 0.025 g (77% of theory)




Mass Spectrum MH


+


181(100)




d3. 3-[2-(2,5-diaminobenzylamino)-1-hydroxyethyl]phenol hydrochloride




Amine Used: 1-(3-hydroxyphenyl)-2-aminoethanol




Yield: 0.025 g (65% of theory)




Mass Spectrum MH


+


274(100)




e3. 2-[(4-methylpyridin-2-ylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 2-picolylamine




Yield: 0.022 g (65% of theory)




Mass Spectrum MH


+


229(100)




f3. 2-(2,5-diaminobenzyl)-1-methyl-1,2,3,4-tetrahydroisoguinoline-6,7-diol hydrochloride




Amine Used: 1-methyl-6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline




Yield: 0.015 g (37% of theory)




Mass Spectrum MH


+


300(100)




g3. 2-(2,5-diaminobenzylamino)-4-methylsulfanylbutyric acid hydrochloride




Amine Used: 2-amino-4-methylmercaptobutyric acid




Yield: 0.015 g (32% of theory)




h3. 1-(2,5-diaminobenzyl)pyrrolidine-2-carboxylic acid hydrochloride




Amine Used: pyrrolidin-2-carboxylic acid




Yield: 0.025 g (72% of theory)




Mass Spectrum MH


+


236(55)




i3. 2-phenylaminomethyl-1,4-diaminobenzene hydrochloride




Amine Used: aniline




Yield: 0.025 g (77% of theory)




Mass Spectrum MH


+


214(100)




j3. 2-(4-dimethylaminophenyl)aminomethyl-1,4-diaminobenzene hydrochloride




Amine Used: 4-amino-N,N-dimethylaniline




Yield: 0.025 g (62% of theory)




Mass Spectrum MH


+


257(100)




k3. 1-[3-(2,5-diaminobenzylamino)phenyl]ethanol hydrochloride




Amine Used: 3-(1-hydroxyethyl)aniline




Yield: 0.025 g (68% of theory)




Mass spectrum MH


+


258(100)




l3. 2-[(3,4-dimethoxyphenylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 3,4-dimethoxyaniline




Yield: 0.025 g (65% of theory)




Mass Spectrum MH


+


274(100)




m3. 2-[(3-fluoro-2-methoxyphenylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 3-fluoro-2-methoxyaniline




Yield: 0.021 g (57% of theory)




Mass Spectrum MH


+


262(100)




n3. 4-chloro-2-(2,5-diaminobenzylamino)phenol hydrochloride




Amine Used: 4-chloro-2-aminophenol




Yield: 0.025 g (67% of theory)




Mass Spectrum MH


+


264(100)




o3. 2-[(4-trifluoromethylphenylamino)methyl]-1,4-diaminobenzene hydrochloride




Amine Used: 4-trifluoromethylaniline




Yield: 0.025 g (64% of theory)




Mass Spectrum MH


+


282(100)




p3. 2-(p-tolylaminomethyl)-1,4-diaminobenzene hydrochloride




Amine Used: 4-methylaniline




Yield: 0.025 g (74% of theory)




Mass Spectrum MH


+


228(100)




Example 2




Synthesis of 2-(1-aminoethyl)-1,4-diaminobenzene Compounds




A. Synthesis of (4-tert.-butoxycarbonylamino-3-(1-hydroxyethyl)phenyl)carbamic acid tert.-butyl ester




3.3 g (0.01 mol) (4-tert.butoxycarbonylamino-3-bromophenyl)carbamic acid-tert.-butyl ester are dissolved in 200 ml diethyl ether under argon. Then first 20 ml of a 1.6 molar methyl lithium solution are added at −25° C. and then 16 ml of a 1.6 molar tert.-butyl lithium solution are added. After one hour 1.2 ml (0.02 mol) of acetaldehyde are added and the reaction mixture is slowly heated to 20° C. After halting the reaction the reaction mixture is hydrolyzed with water, the organic phase is extracted with dilute sodium hydroxide and then dried with magnesium sulfate. The solvent is distilled off in a rotary evaporator and the residue is purified with petroleum ether/acetic acid ethyl ester (8:2). 3.0 g (85% of theoretical) of (4-tert.-butoxycarbonylamino-3-(1-hydroxyethyl)phenyl)carbamic acid-tert.-butyl ester having a melting point of 189° C. are obtained.




B. Synthesis of (4-tert.-butoxycarbonylamino-3-( 1-aminoethyl)phenyl)carbamic acid tert.-butyl ester




3.5 g of the (4-tert.-butoxycarbonylamino-3-(1-hydroxyethyl)phenyl)carbamic acid-tert.-butyl ester (0.01 mol) from step A are dissolved in 30 ml of dichloromethane. Then 1.3 g (0.013 mol) triethylamine and 2.4 g (0.01 mol) mesitylene sulfochloride are added at 4° C. The solution is first stirred for an hour at 4° C. and subsequently stirred for one hour at room temperature. The solvent is distilled off in a rotary evaporator and the residue is purified on silica gel with hexane/ethyl acetate (1:5).




Subsequently the product is dissolved in 30 ml of dimethylsulfoxide and reacted with 3.5 g (0.05 mol) sodium azide and then the reaction mixture is heated to 60° C. After halting the reaction the reaction mixture is poured into ethyl acetate/water and the organic phase is dried with magnesium sulfate. The solvent is distilled off in a rotary evaporator and the residue is purified on silica gel with ethyl acetate/hexane (1:6).




The product obtained is dissolved in ethanol and hydrogenated at 25° C. under addition of 200 mg of a palladium-activated carbon catalyst (10%) and 1.8 g (0.03 mol) acetic acid. After four hours the catalyst is removed by filtration. The solvent is distilled off in a rotary evaporator and the residue is purified on silica gel with chloroform/methanol/triethylamine (50:1 0:1).




1.0 g (28% theoretical) of (4-tert.-butoxycarbonylamino-3-(1-aminoethyl)-phenyl)carbamic acid tert.-butyl ester with a melting point of 170° C. were obtained.




C. Synthesis of 1,4-diamino-2-(1-aminoethyl)benzene Compounds 0.033 g (0.0001 mol) (4-tert.-butoxycarbonylamino-3-(1-aminoethylphenyl)-carbamic acid-tert.-butyl ester from step B and 0.00015 mol of a suitable aldehyde are dissolved in 1,2-dichloroethane. Subsequently 0.1 ml of an acetic acid solution (1M in 1,2-dichloroethane) and 0.06 g (0.0003 mol) NaBH(OAc)


3


are added and the reaction mixture is stirred for 5 to 15 hours. After terminating the reaction the reaction mixture is poured into 10 ml acetic acid ethyl ester, the organic phase is extracted with sodium hydrogen carbonate and then dried with magnesium sulfate. The solvent is distilled off with a rotary evaporator and the residue is purified on silica gel with petroleum ether/ethyl acetate (9:1). The product thus obtained is heated in 4 ml of ethanol at 50° C.




Subsequently 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution is added dropwise to make the hydrochloride. The precipitate is filtered off, washed twice with 1 ml of ethanol and then dried.




a. 1,4-diamino-2-(1-butylaminoethyl)benzene hydrochloride




Aldehyde Derivative Used: butyraldehyde




Yield: 0.025 g (78% of theory)




Mass Spectrum MH


+


208(100)




b. 1,4-diamino-2-{1-(3-methylbutylamino)ethyl}benzene hydrochloride




Aldehyde Derivative Used: 3-methylbutryaldehyde




Yield: 0.025 g (75% of theory)




Mass Spectrum MH


+


222(100)




c. 1,4-diamino-2-(1-benzylaminoethyl)benzene hydrochloride




Aldehyde Derivative Used: benzaldehyde




Yield: 0.025 g (71% of theory)




Mass Spectrum MH


+


242(100)




d. 1,4-diamino-2-{1-[(Pyridin-2-ylmethyl)amino]ethyl}benzene hydrochloride




Aldehyde Derivative Used: pyridin-2-carbaldehyde




Yield: 0.025 g (64% of theory)




Mass Spectrum MH


+


243(20)




e. 1,4-diamino-2-{1-[(pyridin-3-ylmethyl)amino]ethyl}benzene hydrochloride




Aldehyde Derivative Used: pyridin-3-carbaldehyde




Yield: 0.025 g (64% of theory)




Mass Spectrum MH


+


243(50)




f. 1,4-diamino-2-{1-[(pyridin-4-ylmethyl)amino]ethyl}benzene hydrochloride




Aldehyde Derivative Used: pyridin-4-carbaldehyde




Yield: 0.025 g (64% of theory)




Mass Spectrum MH


+


243(100)




g. 1,4-diamino-2{-1-[(thiophen-2-ylmethyl)amino]ethyl}benzene hydrochloride




Aldehyde Derivative Used: thiophen-2-carbaldehyde




Yield: 0.025 g (70% of theory)




Mass Spectrum MH


+


248(100)




h. 1,4-diamino-2-{1-[(thiophen-3-ylmethyl)amino]ethyl}benzene hydrochloride




Aldehyde Derivative Used: thiophen-3-carbaldehyde




Yield: 0.025 g (70% of theory)




Mass Spectrum MH


+


248(100)




i.1,4-diamino-2-{1-(cyclohexylmethylamino)ethyl}benzene hydrochloride




Aldehyde Derivative Used: cyclohexanecarbaldehyde




Yield: 0.025 g (70% of theory)




Mass Spectrum MH


+


248(100)




j. 4-{[1-(2,5-diaminophenyl)ethylamino]methyl}benzene hydrochloride




Aldehyde Derivative Used: 4-hydroxybenzaldehyde




Yield: 0.025 g (68% of theory)




Mass Spectrum MH


+


258(100)




k. 1,4-diamino-2-[1-(4-dimethylaminobenzylamino)ethyl]benzerie hydrochloride




Aldehyde Derivative Used: 4-dimethylaminobenzaldehyde




Yield: 0.020 g (46% of theory)




Mass Spectrum MH


+


285(100)




l. 1,4-diamino-2-(1-(4-nitrobenzylamino)ethyl]benzene hydrochloride




Aldehyde Derivative Used: 4-nitrobenzaldehyde




Yield: 0.025 g (63% of theory)




Mass Spectrum MH


+


286(100)




m. 2-{[1-(2,5-diaminophenyl)ethylamino]methyl}4-nitrophenol hydrochloride




Aldehyde Derivative Used: 2-hydroxy-5-nitrobenzaldehyde




Yield: 0.025 g (60% of theory)




Mass Spectrum MH


+


303(100)




n. 1,4-diamino-2-{1-(4-pyrrolidin-1-ylbenzylamino)ethyl}benzene hydrochloride




Aldehyde Derivative Used: 4-pyrrolidinobenzaldehyde




Yield: 0.025 g (54% of theory)




Mass Spectrum MH


+


311(100)




p. 1,4-diamino-2-{1-[(benzo[1,3]dioxol-5-ylmethyl)amino[ethyl}benzene hydrochloride




Aldehyde Derivative Used: 3,4-methylendioxybenzaldehyde




Yield: 0.025 g (63% of theory)




Mass Spectrum MH


+


286(100)




q. 1,4-diamino-2-{1-(3-chlorobenzylamino)ethyl}benzene hydrochloride




Aldehyde Derivative Used: 3-chlorobenzaldehyde




Yield: 0.025 g (64% of theory)




Mass Spectrum MH


+


276(100)




D. Synthesis of 1,4-diamino-2-(1-aminoethyl)benzene Compounds




0.033 g (0.0001 mol) (4-tert-butoxycarbonylamino-3-(1-aminoethyl)-phenyl)carbamic acid-tert.-butyl ester from step B are dissolved in 25 ml ethanol. Subsequently 0.00015 mol of a suitable fluoro derivative are added. After termination of the reaction the reaction mixture is poured into water, the aqueous phase is extracted with ethyl acetate and then dried with magnesium sulfate. The solvent is distilled off in a rotary evaporator and the residue is purified on silica gel with hexane/ethyl acetate (5:1). The product thus obtained is heated in 4 ml of ethanol at 50° C. Subsequently 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution were added dropwise. The precipitate was filtered off, washed twice with 1 ml of ethanol and then dried.




r. 1,4-diamino-2-[1-(2-nitrophenylamino)ethyl]benzene hydrochloride




Fluoride Derivative Used: 1-fluoro-2-nitrobenzene




Yield: 0.025 g (65% of theory)




Mass Spectrum MH


+


273(100)




s. 1,4-diamino-2-[1-(4-fluoro-2-nitrophenylamino)ethyl]benzene hydrochloride




Fluoride Derivative Used: 1,4-difluoro-3-nitrobenzene




Yield: 0.020 g (50% of theory)




Mass Spectrum MH


+


291 (100)




t. 1,4-diamino-2-[1-(5-fluoro-2-nitrophenylamino)ethyl]benzene hydrochloride




Fluoride Derivative Used: 1,5-difluoro-2-nitrobenzene




Yield: 0.025 g (62% of theory)




u. 1,4-diamino-2-[1-(2-fluoro-6-nitrophenylamino)ethyl]benzene hydrochloride




Fluoride Derivative Used: 1,2-difluoro-6-nitrobenzene




Yield: 0.025 g (62% of theory)




Mass Spectrum MH


+


291(100)




v. 2-[1-(2,5-diaminophenyl)ethylamino]-5-nitrobenzoic acid hydrochloride




Fluoride Derivative Used: 2-fluoro-5-nitrobenzoic acid




Yield: 0.025 g (64% of theory)




Mass Spectrum MH


+


317(100)




w. 1,4-diamino-2-[1-(4-bromo-2-nitrophenylamino)ethyl]benzene hydrochloride




Fluoride Derivative Used: 1-bromo4-fluoro-3-nitrobenzene




Yield: 0.01 8 g (39% of theory)




x. 1,4-diamino-2-[1-(4-amino-2-nitrophenylamino)ethyl]benzene hydrochloride




Fluoride Derivative Used: 1-fluoro-2-nitro-4-aminobenzene




Yield: 0.016 g (36% of theory)




Mass Spectrum MH


+


288(80)




Examples 3 to 70




Oxidation Hair Dye Precursor Compositions




Hair dye precursor solutions with the following compositions were prepared:



















0.0125




mmol




developer substance of formula (I) according to Table I






0.0125




mmol




coupler substance according to Table I






0.01




g




potassium oleate (8 percent aqueous solution)






0.01




g




ammonia (22 percent aqueous solution)






0.01




g




ethanol






0.003




g




ascorbic acid






to 1.0




g




water














1 g of the above-described dye precursor solution is mixed with 1 g of a 6 percent aqueous hydrogen peroxide solution immediately prior to application. Subsequently the mixture is applied to bleached hair. After an acting time of 30 minutes at 40° C. the hair is rinsed with water, washed with a commercially obtained shampoo and dried. The resulting dyed hair colors are tabulated in Table I.












TABLE I











DYED HAIR COLORS OBTAINED WITH THE OXIDATION DYE






PRECURSOR COMPOSITIONS ACCORDING TO THE INVENTION

















Developer





1,3-diamino-4-(2-




5-amino-








Of




1,3-di-hydroxy-




hydroxyethoxy)-




2-methyl








Formula I




benzene




benzene sulfate




phenol




1-naphthol






Example




From Ex.1




coupler




coupler




coupler




coupler



















3




a1




Bright light




Gray-blue




Medium




Gray-rose








Blond





Purple






4




b1




Bright light




Blue




Bright




Bright








Blond





Purple




Gray-rose






5




c1




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






6




d1




Bright blond




Blue




Medium




Bright










Purple




Purple






7




e1




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






8




f1




Bright blond




Blue




Medium




Violet










Purple






9




g1




Bright light




Blue




Medium




Gray-rose








Blond





Purple






10




h1




Bright light




Blue




Medium




Gray-rose








Blond





Purple






11




i1




Bright blond




Blue




Medium




Violet










Purple






12




j1




Bright blond




Blue




Bright




Gray-rose










Purple






13




k1




Bright Blond




Blue




Medium




Gray-rose










Purple






14




l1




Bright light




Blue




Bright




Gray-rose








Blond





Purple






15




m1




Bright light




Blue




Bright




Bright








Blond





Purple




Purple






16




n1




Bright light




Blue




Bright




Gray-rose








Blond





Purple






17




o1




Bright Blond




Blue




Medium




Bright










Purple




Gray-rose






18




p1




Bright light




Blue




Bright




Gray-rose








Blond





Purple






19




q1




Bright light




Blue




Bright




Gray-rose








Blond





Purple






20




r1




Blue




Deep blue




Blue




Deep blue






21




s1




Red-brown




Gray-blue




Gray-rose




Gray-rose






22




t1




Bright rose




Bright




Bright




Gray-rose









Blue-gray




Rose






23




u1




Bright light




Bright Gray-blue




Bright




Bright








Blond





Purple




Gray-rose






24




v1




Bright light




Blue




Bright




Gray-rose








Blond





Purple






25




w1




Bright light




Blue




Bright




Gray-rose








Blond





Purple






26




x1




Bright ash




Blue




Medium




Violet








Blond





Purple






27




y1




Bright Blond




Blue




Medium




Violet










Purple






28




z1




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






29




a2




Gold blond




Gray




Medium




Medium










Purple




Purple






30




b2




Bright light




Blue




Bright




Gray-rose








Blond





Purple






31




c2




Bright blond




Blue




Medium




Gray-rose










Purple






32




d2




Medium purple




Blue




Medium




Violet










Purple






33




e2




Bright light




Blue




Medium




Medium








Blond





Purple




Purple






34




f2




Bright light




Blue




Bright




Gray-rose








Blond





Purple






35




g2




Violet




Deep blue




Violet




Blue






36




h2




Violet




Deep blue




Violet




Violet






37




i2




Deep blue




Deep blue




Gray-rose




Gray-blue






38




j2




Bright light




Gray-blue




Medium




Gray-rose








Blond





Purple






39




k2




Gray-blue




Gray-blue




Gray-blue




Gray-blue






40




l2




Bright Blond




Blue




Medium




Gray-rose










Purple






41




m2




Bright blond




Blue




Medium




Gray-rose










Purple






42




n2




Bright blond




Blue




Medium




Bright










Purple




Gray-rose






43




o2




Bright Blond




Blue




Medium




Gray-rose










Purple






44




p2




Bright Blond




Blue




Medium




Gray-rose










Purple






45




q2




Bright light




Blue




Medium




Bright








Blond





Purple




Gray-rose






46




r2




Bright blond




Deep blue




Purple




Violet






47




s2




Bright light




Bright




Bright




Bright








Blond




Gray-blue




Purple




Rose






48




t2




Bright light




Blue




Medium




Gray-rose








Blond





Purple






49




u2




Bright light




Gray-blue




Medium




Gray-rose








Blond





Purple






50




v2




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






51




w2




Bright Purple




Bright gray




Bright




Bright










Purple




Purple






52




x2




Bright ash




Gray-blue




Not available




Gray-rose








Blond






53




y2




Bright light




Gray-blue




Bright




Bright








Blond





Purple




Gray-rose






54




z2




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






55




a3




Bright light




Blue




Bright




Bright








Blond





Purple




Purple






56




b3




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






57




c3




Bright light




Gray-blue




Purple




Gray-rose








Blond








58




d3




Bright light




Gray-blue




Medium




Gray-rose








Blond





Purple






59




e3




Bright Blond




Deep blue




Medium




Violet










Purple






60




f3




Bright light




Bright




Bright




Gray-rose








Blond




Gray-blue




Purple






61




g3




Bright light




Bright




Bright




Bright








Blond




Gray-blue




Rose




Gray-rose






62




h3




Bright light




Gray-rose




Bright




Bright








Blond





Purple




Gray-rose






63




i3




Bright Blond




Deep blue




Medium




Violet










Purple






64




j3




Bright ash




Gray-blue




Purple




Gray-rose








Blond






65




k3




Bright ash




Blue




Medium




Violet








Blond





Purple






66




l3




Gray




Blue




Violet




Gray-rose






67




m3




Bright Blond




Blue




Medium




Violet










Purple






68




n3




Bright Blond




Gray-blue




Gray




Gray-rose










Purple






69




o3




Bright Blond




Blue




Medium




Bright










Purple




Violet






70




p3




Bright Blond




Blue




Medium




Violet










Purple














Examples 71 to 80




Oxidation Hair Dye Precursor Compositions




Hair dye precursor solutions with the following compositions were prepared:



















X




g




developer substances E1 to E1″ of formula (I)








according to Table II






U




g




developer substances E2 to E9 according to Table II






Y




g




coupler substances K11 to K36 according to Table IV






Z




g




direct-dyeing dye compounds D1 to D3 according to








Table III






10.000




g




potassium oleate (8 percent aqueous solution)






10.000




g




ammonia (22 percent aqueous solution)






10.000




g




ethanol






0.300




g




ascorbic acid






to 100.000




g




water














30 g of the above-described dye precursor solution are mixed with 30 g of a 6 percent aqueous hydrogen peroxide solution immediately prior to application. Subsequently the mixture is applied to hair. After an acting time of 30 minutes at 40° C. the hair is rinsed with water, washed with a commercially obtained shampoo and dried. The resulting dyed hair colors are given in Table V.




Examples 81 to 86




Oxidation Hair Dye Precursor Compositions




Hair dye precursor creams with the following compositions were prepared:



















X




g




developer substances E1 to E1″ of formula (I)








according to Table II






Y




g




coupler substances K11 to K36 according to Table IV






Z




g




direct-dyeing dye compound D2 according to Table III






15.0




g




cetyl alcohol






0.3




g




ascorbic acid






3.5




g




sodium lauryl alcohol diglycol ether sulfate,








28% aqueous solution






3.0




g




ammonia, 22% aqueous solution






0.3




g




sodium sulfite, water-free






to 100




g




water














30 g of the above-described dye precursor cream are mixed with 30 g of a 6 percent aqueous hydrogen peroxide solution immediately prior to application. Subsequently the mixture is applied to hair. After an acting time of 30 minutes the hair is rinsed with water, washed with a commercially obtained shampoo and dried. The resulting dyed hair colors are given in Tables VI.




Examples 87 to 110




Oxidation Hair Dye Precursor Compositions




Hair dye precursor solutions with the following compositions were prepared:



















0.0125




mmol




developer substance of formula (I) according to Table








VII






0.0125




mmol




coupler substance according to Table VII






0.01




g




potassium oleate (8 percent aqueous solution)






0.01




g




ammonia (22 percent aqueous solution)






0.01




g




ethanol






0.003




g




ascorbic acid






to 1.0




g




water














1 g of the above-described dye precursor solution is mixed with 1 g of a 6 percent aqueous hydrogen peroxide solution immediately prior to application. Subsequently the mixture is applied to bleached hair. After an acting time of 30 minutes at 40° C. the hair is rinsed with water, washed with a commercially obtained shampoo and dried. The resulting dyed hair colors are tabulated in Table VII.












TABLE II









DEVELOPER SUBSTANCES
























E1




2-phenylaminomethyl-1,4-diaminobenzene hydrochloride







(according to example 1, i3)






E1′




2-[(4-methylpyridin-2-ylamino)methyl]-1,4-diaminobenzene







hydrochloride (according to example 1, e3)






E1″




2-[(2,5-diaminobenzyl)-(2-hydroxyethyl)amino]ethanol







hydrochloride (according to example 1, l2)






E2




1,4-diaminobenzene






E3




2,5-diaminophenylethanol sulfate






E4




3-methyl-4-aminophenol






E5




4-amino-2-aminomethylphenol dihydrochloride






E6




4-aminophenol






E7




N,N-bis(2′-hydroxyethyl)-p-phenylenediamine sulfate






E8




4,5-diamino-1-(2′-hydroxyethyl)pyrazole sulfate






E9




2,5-diaminotoluene sulfate






















TABLE II









DEVELOPER SUBSTANCES
























E1




2-phenylaminomethyl-1,4-diaminobenzene hydrochloride







(according to example 1, i3)






E1′




2-[(4-methylpyridin-2-ylamino)methyl]-1,4-diaminobenzene







hydrochloride (according to example 1, e3)






E1″




2-[(2,5-diaminobenzyl)-(2-hydroxyethyl)amino]ethanol







hydrochloride (according to example 1, l2)






E2




1,4-diaminobenzene






E3




2,5-diaminophenylethanol sulfate






E4




3-methyl-4-aminophenol






E5




4-amino-2-aminomethylphenol dihydrochloride






E6




4-aminophenol






E7




N,N-bis(2′-hydroxyethyl)-p-phenylenediamine sulfate






E8




4,5-diamino-1-(2′-hydroxyethyl)pyrazole sulfate






E9




2,5-diaminotoluene sulfate






















TABLE IV









DEVELOPER SUBSTANCES


























K11




1,3-diaminobenzene







K12




2-amino-4-(2′-hydroxyethyl)aminoanisole sulfate







K13




1,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate







K14




2,4-diamino-5-fluorotoluene sulfate







K15




3-amino-2-methylamino-methoxypyridine







K16




3,5-diamino-2,6-dimethoxypyridine dihydrochloride







K17




2,4-diamino-5-ethoxytoluene sulfate







K18




N-(3-dimethylamino)phenylurea







K19




1,3-bis-(2,4-diaminophenoxy)propane tetrahydrochloride







K21




3-aminophenol







K22




5-amino-2-methylphenol







K23




3-amino-2-chloro-6-methylphenol







K24




5-amino-4-fluoro-2-methylphenol sulfate







K25




1-naphthol







K26




1-acetoxy-2-methylnaphthalene







K31




1,3-dihydroxybenzene







K32




2-methyl-1,3-dihydroxybenzene







k33




1-chloro-2,4-dihydroxybenzene







K34




4-(2′-hydroxyethyl)amino-1,2-methylenedioxybenzene








Hydrochloride







K35




3,4-methylenedioxyphenol







K36




2-amino-5-methylphenol























TABLE V











HAIR DYE PRECURSOR COMPOSITIONS AND DYED






HAIR COLORS OBTAINED THEREWITH















Exemplary










Dyestuff*




71




72




73




74









E1




0.35






0.30






E1′





0.30






E1″






0.30






E4




0.30






E5





0.30






E6






0.30






E8







0.30






K31




0.18






0.20






K32





0.22






K33






0.20






K25




0.30




0.30





0.30






K26






0.35






Dyed Hair




Red-brown




Red-brown




Red-brown




Red-brown






Color











*amounts of dyestuffs are in grams





















TABLE V











(CON): HAIR DYE PRECURSOR COMPOSITIONS AND






DYED HAIR COLORS OBTAINED THEREWITH

















Exemplary












Dyestuff*




75




76




77




78




79




80









E1




0.50






0.16








E1′





0.40






0.15






E1″






0.40






0.15






E2







0.15






E3








0.15






E9









0.15






K12






0.10






K13




0.09




0.09






K31




0.20






0.15




0.20




0.10






K32





0.20





0.10





0.10






K33






0.20






K21




0.05







K22





0.05






K23






0.05




0.10




0.10




0.10






Dyed Hair




Blond




Blond




Blond




Blond




Blond




Blond






Color











*amounts of dyestuffs are in grams





















TABLE VI











HAIR DYE PRECURSOR COMPOSITIONS AND DYED






HAIR COLORS OBTAINED THEREWITH

















Exemplary












Dyestuff*




81




82




83




84




85




86









E1




2.50






0.90








E1′





2.50






0.90






E1″






2.50






0.90






K12







0.10




0.10




0.10






K13




1.10




1.10




1.10






K31




1.10




1.10




1.10




0.40




0.40




0.40






D2







0.10




0.10




0.10






K23






0.05




0.10




0.10




0.10






Dyed Hair




Black




Black




Black




Brown




Brown




Brown






Colors











*amounts of dyestuffs are in grams





















TABLE VII











DYED HAIR COLORS OBTAINED WITH THE OXIDATION DYE






PRECURSOR COMPOSITIONS ACCORDING TO THE INVENTION

















Developer





1,3-diamino-4-(2-




5-amino-








Of




1,3-dihydroxy-




hydroxyethoxy)-




2-methyl








Formula I




benzene




benzene sulfate




phenol




1-naphthol






Example




From Ex.2




coupler




coupler




coupler




coupler



















87




a




Bright light




Gray-blue




Purple




Gray-rose








Blond






88




b




Bright light




Blue




Bright




Gray-rose








Blond





Purple






89




c




Bright light




Gray-blue




Purple




Gray-rose








Blond






90




d




Bright blond




Blue




Medium




Violet










Purple






91




e




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






92




f




Bright blond




Blue




Medium




Gray-










Purple




Violet






93




g




Bright light




Gray-blue




Bright




Gray-rose








Blond





Purple






94




h




Bright Blond




Gray-blue




Purple




Violet






95




i




Bright blond




Gray-blue




Bright Purple




Bright











Violet






96




j




Bright blond




Blue




Medium




Gray-rose










Purple






97




k




Bright light




Blue




Bright




Gray-rose








Blond





Purple






98




l




Bright Blond




Blue




Purple




Violet






99




m




Yellow




Brown




Red-brown




Red-brown






100




n




Bright light




Gray




Bright




Bright








Blond





Purple




Violet






101




o




Bright Blond




Blue




Medium




Bright










Purple




Gray-rose






102




p




Bright light




Gray-blue




Bright




Bright








Blond





Purple




Violet






103




q




Bright light




Gray-blue




Bright




Bright








Blond





Purple




Violet






104




r




Bright blond




Gray




Red wine




Gray-black






105




s




Green




Blue-black




Red wine




Gray






106




t




Bright blond




Gray-blue




Bright




Gray










Purple






107




u




Bright light




Gray-blue




Medium




Bright








Blond





Purple




Gray-rose






108




v




Bright light




Gray-blue




Red-brown




Gray








Blond







109




W




Bright light




Gray-blue




Medium




Gray








Blond





Purple






110




X




Bright Purple




Bluish red




Medium




Violet










Purple














Unless otherwise indicated all percentages are percentages by weight.




The disclosure in German Patent Application 199 61 272.2 of Dec. 18, 1999 is incorporated here by reference. This German Patent Application describes the invention described hereinabove and claimed in the claims appended hereinbelow and provides the basis for a claim of priority for the instant invention under 35 U.S.C. 119.




While the invention has been illustrated and described as embodied in substituted 2-aminoalkyl-1,4-diaminobenzene compounds and dye compositions containing same, it is not intended to be limited to the details shown, since various modifications and changes may be made without departing in any way from the spirit of the present invention.




Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention.




What is claimed is new and is set forth in the following appended claims.



Claims
  • 1. An oxidation dye precursor composition for oxidative dyeing of keratin fibers, said dye precursor composition comprising at least one developer compound and at least one coupler compound;wherein said at least one coupler compound is selected from the group consisting of 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)-amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene, 2-amino-1-(2-hydroxyethoxy)-4-methyl-aminobenzene, 2,4-diaminophenoxyacetic acid, 3-[(di(2-hydroxyethyl)-amino]-aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]-aniline, 3-[(2-amino-ethyl)-amino]aniline, 1,3-di(2,4-diaminophenoxy)propane, di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dicholorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2-{(3-hydroxyphenyl)-amino}acetamide, 5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)-aminophenol, 3-[(2-methoxyethyl)amino]phenol, 5-amino-2-ethylphenol, 2-(4-amino-2-hydroxy-phenoxy)ethanol, 5-[(3-hydroxypropyl)amino]-2-methylphenol, 3-[(2,3-dihydroxy-propyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)-amino]-2-methylphenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate, 1,3-dihydoxybenzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole and 2,3-indolindione; and wherein said at least one developer compound includes at least one substituted 2-aminoalkyl-1,4-diaminobenzene compound of the formula (I): whereinR1, R2, R3 and R4, independently of each other, are each hydrogen, a C1- to C6-alkyl group, a C1- to C4-hydroxyalkyl group, a C2- to C4-dihydroxyalkyl group or a C1- to C4-alkoxy-(C1- to C2-)alkyl group, or R1 and R2 together with N form a four member to eight member aliphatic ring; wherein at least two of said R1, R2, R3 and R4 represent hydrogen and wherein R3 and R4 are not both simultaneously a C1- to C6-alkyl group; R5 represents hydrogen, a halogen atom, a C1- to C4-alkyl group, a C1- to C4-hydroxyalkyl group or a C1- to C4-alkoxy group; R6 and R7, independently of each other, each represent hydrogen, a C1- to C2-alkoxy group, a C1- to C6-alkyl group, a C1- to C6-alkenyl group, a C1- to C4-hydroxyalkyl group, a C3- to C4-dihydroxyalkyl group, a C1- to C4-aminoalkyl group, a C1- to C4-dimethylaminoalkyl group, a C1- to C4-acetylaminoalkyl group, a C1- to C4-methoxyalkyl group, a C1- to C4-ethoxyalkyl group, a C1- to C4-cyanoalkyl group, a C1- to C4-carboxyalkyl group, a C1- to C4-aminocarbonylalkyl group, a pyridylmethyl group, a furfuryl group, a hydrogenated furfuryl group, a substituted pyridyl group, a group of the formula II: a group of the formula III: a group of the formula IV: wherein at least one of R6 and R7 is not hydrogen or R6 and R7 together with N form one of the following rings: R8 represents hydrogen or a C1- to C6-alkyl group; R9 represents hydrogen, a carboxy group or an aminocarbonyl group; R10 and R11, independently of each other, each represent hydrogen, a hydroxy group, an aminocarbonyl group, a methylthiomethyl group, a substituted phenyl group having a phenyl group substituent or a hydroxy group substitutent or a group of the formula: whereinR12, R13, R14, R15 and R16 are each, independently of each other, hydrogen, a halogen atom, a cyano group, a hydroxy group, a C1- to C4-alkoxy group, a C1- to C4-hydroxyalkoxy group, a C1- to C6-alkyl group, a C1- to C4-alkylthioether group, a mercapto group, a nitro group, an amino group, an alkylamino group, a hydroxyalkylamino group, a dialkylamino group, a di(hydroxyalkyl)amino group, a (dihydroxyalkyl)amino group, a (hydroxyalkyl)-alkylamino group, a trifluoromethane group, a —C(O)H group, a —C(O)CH3 group, a —C(O)CF3 group, a —Si(CH3)3 group, a C1- to C4-hydroxyalkyl group, a C3- to C4-dihydoxyalkyl group, or two of the groups R12 to R16 next to each other form an —O—CH2—O— bridge; R17 represents a C1- to C4-alkyl group or a C1- to C4-hydroxyalkyl group; R18 represents hydrogen or a C1- to C6-alkyl group; R19 represents one or more hydrogen, hydroxy, carboxy, aminocarbonyl or hydroxymethyl group or groups; and R20 represents hydrogen or a C1- to C6-alkyl group, with the proviso that R1, R2 and R8 are not each hydrogen when (i) R5 is in the 5-position of the aromatic ring and R5 is hydrogen, a C1- to C4-alkyl group or a halogen atom, and when (ii) R6 and R7, independently of each other, are a C1- to C4-alkyl group or a phenyl group; or a physiologically compatible, water-soluble salt of said at least one substituted 2-aminoalkyl-1,4-diaminobenzene compound of the formula (I).
  • 2. The oxidation dye precursor composition as defined in claim 1, wherein said at least one substituted 2-aminoalkyl-1,4-diaminobenzene compound of the formula (I) is selected from the group consisting of 2-(2,3-dihydroxypropyl)-aminomethyl-1,4-diamino-benzene; 2-[(2-aminoethylamino)methyl]-1,4-diaminobenzene; 2-[(2-hydroxy-ethylamino)methyl]-1,4-diaminobenzene; 2-[(2,5-diaminobenzyl)methylamino]-ethanol; 2-(2,5-diaminobenzylamino)-propan-1-ol; 2-[(2,5-diaminobenzyl)-(2-hydroxyethyl)amino]ethanol; [1-(2,5-diaminobenzyl)-pyrrolidin-2-yl]methanol; 1-(2,5-diaminobenzyl)-pyrrolidin-2-carboxamide; 2-[(4-methylpyridin-2-yl-amino)-methyl]-1,4-diaminobenzene; 2-((2-aminophenylamino)methyl)-1,4-diamino-benzene; 2-((2-chlorophenylamino)methyl)-1,4-diaminobenzene; 2-((2-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-fluoro-phenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyethylaminophenyl-amino)methyl)-1,4-diaminobenzene; 2-((2-N,N-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-pyrrolidinphenylamino)methyl)-1,4-diaminobenzene; 2-((3-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-chlorophenylamino)methyl)-1,4-diaminobenzene; 2-((3-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-fluorophenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-N,N-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-pyrrolidin-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-chlorophenylamino)methyl)-1,4-diaminobenzene; 2-((4-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-fluorophenylamino)methyl)-1,4-diaminobenzene; 2-((4-hydroxyethylaminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-N,N-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-pyrrolidinphenylamino)methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxy)-ethoxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-amino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-chloro-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyethylamino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((2-methyl-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxy)-ethoxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-amino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-chloro-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxy-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxyethylamino-4-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-methyl-4-aminophenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxy)ethoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((2-hydroxyphenylamino)methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxy)ethoxyphenylamino)methyl)-1,4-diaminobenzene; 2-((3-hydroxyphenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxy)-ethoxy-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-hydroxyphenylamino)methyl)-1,4-diaminobenzene; 2-(phenylamino)methyl-1,4-diaminobenzene; 2-[5-amino-4-(2,5-diaminophenylamino)-pyrazol-1-yl]ethanol; N2-(5-amino-1-methyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene; N2-(5-amino-1-isopropyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene and N2-(5-amino-1,3-dimethyl-1H-pyrazol-4-yl)-1,2,4-triaminobenzene.
  • 3. The oxidation dye precursor composition as defined in claim 1, containing from 0.005 to 20.0 percent by weight of said at least one substituted 2-aminoalkyl-1,4-diaminobenzene compound of the formula (I).
  • 4. The oxidation dye precursor composition as defined in claim 1, containing at least one direct-dyeing dye compound.
  • 5. The oxidation dye precursor composition as defined in claim 1, wherein said at least one developer compound includes at least one member selected from the group consisting of 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, 4-aminophenol, derivatives of said 4-aminophenol, derivatives of 4,5-diaminopyrazole and tetraaminopyrimidine compounds.
  • 6. The oxidation dye precursor composition as defined in claim 5, containing from 0.005 to 20 percent by weight of said at least one developer compound, based on a total amount of said dye precursor composition.
  • 7. The oxidation dye precursor composition as defined in claim 1, containing from 0.0005 to 20 percent by weight of at least one coupler compound, based on a total amount of said dye precursor composition.
  • 8. The oxidation dye precursor composition as defined in claim 4, wherein said at least one direct-dyeing dye compound is selected from the group consisting of triphenylmethane direct-dyeing dye compounds, aromatic nitro direct-dyeing dye compounds, direct-dyeing azo dye compounds and direct-dyeing anthraquinone dye compounds.
  • 9. The oxidation dye precursor composition as defined in claim 1, in the form of a solution, cream, emulsion or gel, and further comprising at least one cosmetic additive ingredient selected from the group consisting of solvents, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, thickeners and care materials.
  • 10. The oxidation dye precursor composition as defined in claim 1, wherein the keratin fibers to be dyed are hair.
Priority Claims (1)
Number Date Country Kind
199 61 272 Dec 1999 DE
US Referenced Citations (9)
Number Name Date Kind
3743509 Baltazzi Jul 1973 A
4149848 Bugat et al. Apr 1979 A
4797130 Clausen et al. Jan 1989 A
5019130 Flood May 1991 A
5851237 Anderson et al. Dec 1998 A
5876464 Lim et al. Mar 1999 A
6042620 Braun et al. Mar 2000 A
6106578 Jones Sep 2000 A
6132475 Chassot et al. Oct 2000 A
Foreign Referenced Citations (2)
Number Date Country
199 61 274 Feb 2001 DE
199 61 229 Apr 2001 DE
Non-Patent Literature Citations (2)
Entry
Monografie Von K. H. Schrader: “Grundlagen Und Rezepturen Der Kosmetika”, 2. Auflage (1989), pp. 784-799.
“Protective Groups”, In Organic Synthesis, Kapitel 7, Wiley Interscience, 1991.