DE20202609U1 - Colorants containing (1,1'-biphenyl) -3,5-diamine derivatives and new (1,1'-biphenyl) -3,5-diamine derivatives - Google Patents

Description

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Description

Dyes containing [1,1'-biphenyl]-3,5-diamine derivatives and new [1,1'-biphenyl]-3,5-diamine derivatives

The present invention relates to agents for the oxidative coloration of keratin fibers, in particular human hair, based on a developer substance/coupler substance combination which contains [1,1'-biphenyl]-3,5-diamine derivatives as coupler substance, as well as new [1,1'-biphenyl]-3,5-diamine derivatives.

Oxidation dyes have become very important in the field of coloring keratin fibers, especially hair coloring. The coloring is created by the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent. The developer substances used are in particular 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, p-aminophenol and 4,5-diaminopyrazole derivatives, while the coupler substances used include resorcinol, 4-chlororesorcinol, 1-naphthol, 3-aminophenol and derivatives of m-phenylenediamine.

In addition to the desired intensity, oxidation dyes used to dye human hair must meet numerous additional requirements. The dyes must be safe from a toxicological and dermatological point of view and the hair dyes produced must have good lightfastness, perm fastness, acid fastness and rubbing fastness. In any case, however,

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Such dyes must remain stable for a period of at least 4 to 6 weeks without the effects of light, friction and chemical agents. It is also necessary that a wide range of different color nuances can be produced by combining suitable developer substances and coupler substances. To produce copper-colored shades, combinations of m-aminophenol or its derivatives with certain developer substances are generally required. However, since only compounds that satisfy the requirements for consumer protection and that produce stable colors over a longer period of time can be used for hair coloring, the choice of suitable developer substances and coupler substances is limited. The use of 5-substituted m-phenylenediamines in oxidation hair dyes is known from DE-OS 35 08 309 and DE-OS 38 24 299. However, with the dyes currently known, it is not possible to meet all of the requirements placed on a dye in all respects.

There was therefore still a need for new coupling substances which meet the above-mentioned requirements to a particularly high degree.

It has now been found that when [1,1'-biphenyl]-3,5-diamine derivatives of the general formula (I) are used as a coupler substance, stable copper-colored to purple color nuances are obtained.

The present invention therefore relates to an agent for the oxidative coloration of keratin fibers, such as wool, fur, feathers or hair, in particular human hair, based on a

A developer-coupler combination which contains as coupler at least one [1,1'-biphenyl]-3,5-diamine derivative of formula (I) or its salt with an inorganic or organic acid,

R4

(I)

R1 is hydrogen, a halogen atom (fluorine, chlorine, bromine, iodine), a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ hydroxyalkoxy group, a C _r C ₆ alkyl group, a C ₁ -C ₄ alkylthioether group, a trifluoromethane group, a -Si(CH ₃ ) ₃ group, a C ₁ -C ₄ hydroxyalkyl group or a C ₂ -C ₄ dihydroxyalkyl group;

R2,R3,R4,R5,R6 can be the same or different and independently of one another represent hydrogen, a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, a hydroxy group, a C _T -C ₄ -alkoxy group, a C^C^hydroxyalkoxy group, a C ₁ -C ₆ -AIKyIgOiPPe, a C ₁ -C ₄ -AIkVI-thioether group, a mercapto group, a nitro group, an amino group (NH2), a C _r C ₄ -monoalkylamino group, a DKC^C^J-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 -C ₄ -hydroxyalkyl group, a C ₂ -C ₄ dihydroxyalkyl group, a -CH=CHR7 group, a -(CH ₂ ) _p -CO ₂ R8 group or a -(CH ₂ ) _P -R9 group with p= 1,2,3 or 4, a -C(R10)=NR11 group or a

C(R13)H-NR14R15 group, or two adjacent radicals R2 to R6 form an -O-CH2-O- bridge; R7 is hydrogen, a nitro group, a CO ₂ R8 group or a -C(O)CH ₃ group;

R8, R10 and R13 may be the same or different and are independently hydrogen or a C^C^alkyl group; R9 is an amino group or a nitrile group; R11, R14 and R15 may be the same or different and are independently hydrogen, a hydroxy group, a G _r C ₄ -alkyl group, a C^-C^hydroxyalkyl group, a C ₂ -C ₄ -dihydroxyalkyl-

group or a radical of the formula ^=^; R12 is hydrogen, an amino group or a hydroxy group; with the proviso that the compound of formula (I) does not have an inversion centre.

Examples of compounds of formula (I) which may be mentioned are: biphenyl-3,5-diamine; 2-(3,4' ^- diamino-5-methyl-biphenyl-2-yloxy)-ethanol, ^3'- amino-2'-(2-hydroxy-ethoxy)-5' ^- methyl-biphenyl-4-ol, 2-(3-amino-5-methyl-:biphenyl-2-yloxy)-ethanol, 4-benzo[1,3]dioxol-5-yl-benzene-1,3-diamine; 2'-(2-hydroxyethyl)-biphenyl-3,5-diamine;2'- ^acetyl -biphenyl-3,5-diamine; 2'-amino-biphenyl-3,5-diamine;2'- ^bromo -biphenyl-3,5-diamine; 2'-chloro-biphenyl-3,5-diamine;2'-cyano-biphenyl-3,5-diamine;2'-ethylbiphenyl-3,5-diamine;2'-fluorobiphenyl-3,5-diamine; 2 ^I -Hydroxy-biphenyl-3,5-diamine; 2'-Methoxy-biphenyl-3,5-diamine; 2 ^I -Methyl-biphenyl-3,5-diamine; 2 ¹ -Methylsulfanylbiphenyl-3,5-diamine; 2'-nitro-biphenyl-3,5-diamine; 2 ^t -Trifluoromethyl-biphenyl-3,5-diamine; 3'-(2-Hydroxyethyl)-biphenyl-3,5-diamine;S'-acetyl-biphenyl-S.ö-diamine;3'-Aminobiphenyl

3,5-diamine; 3'-Bromobiphenyl-3,5-diamine;S'-Chloro-biphenyl-S.ö-diamine;3'-cyanobiphenyl-3,5-diamine;3'-Ethyl-biphenyl-3,5-diamine;3'- ^{1Fluorbiphenyl} -3,5-diamine; S'-Hydroxy-biphenyl-SS-diamine;3'-Methoxybiphenyl-3,5-diamine;3'-Methyl-biphenyl-3,5-diamine;3'-Methylsulfanylbiphenyl-3,5-diamine;3'-Nitro-biphenyl-3,5-diamine;S'-trifluoromethylbiphenyl-3,5-diamine;4'-(2-Hydroxyethyl)-biphenyl-3,5-diamine;4'-acetylbiphenyl-3,5-diamine; 4 ¹ -Amino-biphenyl-3,5-diamine; 4'-bromobiphenyl-3,5-diamine; 4 ^I -Chloro-biphenyl-3,5-diamine; 4 ¹ -cyanobiphenyl-3,5-diamine; 4 ^l -Ethyl-biphenyl-3,5-diamine; 4 ^I -fluorobiphenyl-3,5-diamine; 4'-Hydroxybiphenyl-3,5-diamine;4'-Methoxy-biphenyl-3,5-diamine;4'-Methyl-biphenyl-3,5-diamine;4'-Methylsulfanylbiphenyl-3,5-diamine;4'-nitro-biphenyl-3,5-diamine;4'-Trifluoromethyl-biphenyl-3,5-diamine;2'-amino-3'-aminobiphenyl-3,5-diamine; 2 ¹ -Amino-3'-hydroxy-biphenyl-3,5-diamine;2'-Amino-3'-methoxy-biphenyl-3,5-diamine;2'-Amino-3'-nethyl-biphenyl-3,5-diamine;2'-&Agr;&Ggr;&eegr;&idigr;&eegr;&ogr;-4'-3&iacgr;&eegr;&idigr;&eegr;&ogr;-&Mgr;&rgr;&Mgr;&thgr;&eegr;&ngr;&Igr;-3,5-&agr;&Idigr;3&Ggr;&eegr;&idiagr;&eegr;;2'-amino-4'-hydroxy-biphenyl-3,5-diamine;2'-Amino-4'-methoxy-biphenyl-3,5-diamine;2'-Amino-4'-methyl-biphenyl-3,5-diamine;2'-amino-5'-amino-biphenyl-3,5-diamine;2'-Amino-5'-hydroxy-biphenyl-3,5-diamine; 2 ¹ -Amino-5'-methoxy-biphenyl-3,5-diamine;2'-Amino-5'-methyl-biphenyl-3,5-diamine;2'-Amino-6 ^I -aminobiphenyl-3,5-diamine; 2'-Amino-6'-hydroxy-biphenyl-3,5-diamine;2'-Amino-6'-methoxy-biphenyl-3,5-diamine; 2 ^> -Amino-6 ^l -methyl-biphenyl-3,5-diamine; 2'-Hydroxy-3'-amino-biphenyl-3,5-diamine; 2 ¹ -Hydroxy-3'-hydroxy-biphenyl-3,5-diamine;2'-Hydroxy-3'-methoxy-biphenyl-3,5-dtamine;2'-Hydroxy-3'-methyl-biphenyl-3,5-diamine; 2 ^I -Hydroxy-4 ¹ -amino-biphenyl-3,5-diamine; 2 ^l -Hydroxy-4'-hydroxy-blphenyl-3,5-diannine;2'-;Hydroxy-4'-methoxybiphenyl-3,5-diamine; 2 ^l -Hydroxy-4 ^I -methyl-biphenyl-3,5-diamine;

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2 ¹ -Hydroxy-5 ^> -amino-biphenyl-3,5-diamine; 2 ^I -Hydroxy-5'-hydroxy-biphenyl-3,5-diamine;2'-Hydroxy-5'-methoxy-biphenyl-3,5-diamine;2'-Hydroxy-5'-methyl-biphenyl-3,5-diamine;2'-Hydroxy-6'-amino-biphenyl-3,5-diamine;2'-Hydroxy-6'-hydroxy-biphenyl-3,5-diamine; 2 ¹ -Hydroxy-6'-methoxybiphenyl-3,5-diamine; 2 ^I -Hydroxy-6 ^l -methyl-biphenyl-3,5-diamln; 2'-Methoxy-3'-amino-biphenyl-3,5-diamine; 2 ^l -Methoxy-3'-hydroxybiphenyl-3,5-diamine;^'-Methoxy-S'-methoxy-biphenyl-SS-diamine; 2 ^l -Methoxy-3'-methyl-biphenyl-3,5-diamine; 2 ^I -Methoxy-4 ¹ -amino-biphenyl-3,5-diamine; 2 ^l -Methoxy-4'-hydroxy-biphenyl-3,5-diamine;2'-Methoxy-4'-imethoxy-biphenyl-3,5-diamine;2'-Methoxy-4'-methyl-biphenyl-3_>5-diamine;2'-Methoxy-5'-amino-biphenyl-3,5-diamine;2'-Methoxy-5'-hydroxybi _: phenyl-3,5-d.iamine; 2'-Methoxy-5'-methoxy-biphenyl-3,5-diamine; 2 ^I -Methoxy-5'-methyl-biphenyl-3,5-diamine; 2 ^l -Methoxy-6 ^I -amino-biphenyl-3,5-diarnine; 2'-Methoxy-6 ^I -hydroxy-biphenyl-3,5-diarnine; 2'-Methoxy-6 ^I -methoxy-biphenyl-3,5-diamine; ^-Methoxy-e'-methyl-biphenyl-SS-diamine;2'-Methyl- ^3I -amino-biphenyl-3,5-diamine; 2'-Methyl-3'-hydroxy-biphenyl-3,5-diamine; 2 ¹ -Methyl-3 ^l -methoxy-biphenyl-3,5-diamine; 2 ^I -Methyl-3'-methyl-biphenyl-3,5-diamine; 2 ^I -Methyl-4 ^I -amino-biphenyl-3,5-diamine; 2 ¹ -Methyl-4'-hydroxy-biphenyl-3,5-diamine;2'-Methyl-4'-methoxy-biphenyl-3,5-diamine;2'-Methyl-4'-methyl-biphenyl-3,5-diamine;2'-Methyl-5'-aminobi:phenyl-3,5-diamine;2'-Methyl-5'-hydroxy-biphenyl-3,5-diamine; 2 ^> -Methyl-5'-methoxy-biphenyl-3,5-diannine;2'-methyl-5'-nethyl-biphenyl-3,5-diamine; 2 ¹ -Methyl-6'-amino-biphenyl-3,5-diannine;2'-Methyl-6'-hydroxy-biphenyl-3,5-diamine;Z-methyt-e'-methoxy-biphenyl-S^-diamine; 2 ¹ -Methyl-6 ¹ -methyl-biphenyl-3,5-diamine; S'-amino-^-amino-biphenyl-SS-diamine;.S'-Amino^'-hydroxy-biphenyl-SS-diamine;3'-Amino-4' ^? -methoxy-b|phenyl-3,5-diamine; S'-Amino^'-methyl-biphenyl-SS-diamine;3'-αηπΩ-biphenyl-3,5-diamine;S'-amino-S'-hydroxy-biphenyl-SS-diamine; 3-amino

5 ^f -methoxy-biphenyl-3,5-diamine; 3'-Amino-5'-methyl-biphenyl-3,5-diamine;S'-Hydroxy^'-amino-biphenyl-SS-diamine;3'-Hydroxy-4'-hydroxy-biphenyl-3,5-diamine;S'-Hydroxy^'-methoxy-biphenyl-SS-diannine;3'-Hydroxy-4'-methyl-biphenyl-3,5-diamine;S'-Hydroxy-δ-amino-biphenyl-SS-diamine;S'-Hydroxy-S'-hydroxy-biphenyl-SS-diamine;S'-Hydroxy-δ-methoxybiphenyl-3,5-diamine;S'-Hydroxy-S'-methyl-biphenyl-SS-diamine;S'-Methoxy^'-amino-biphenyl-S.ö-diamine;3'-Methoxy-4'-hydroxybiphenyl-3,5-diamine;S'-Methoxy^'-methoxy-biphenyl-SS-diamine;3'-Methoxy-4'-methyl-biphenyl-3,5-diamine;S'-Methoxy-S'-amino-biphenyl-3,5-diamine;S'-Methoxy-S'-hydroxy-biphenyl-S.ö-diamine;3'-Methoxy-5'-methoxy-biphenyl-3,5-diamine;3'-Methoxy-5'-methyl-biphenyl-3,5-diamine;3'-Methyl-4'-amino-biphenyl-3,5-diamine;3'-Methyl-4'-hydroxy-biphenyl-3,5-diamine;S'-Methyl^'-methoxy-biphenyl-SS-diamine;3'-Methyl-4'-methyl-biphenyl-3,5-diamine;S'-Methyl-S'-amino-biphenyl-SS-diamine;S'-methyl-S'-hydroxy-biphenyl-SS-diamine;3'-Methyl-5'-methoxy-biphenyl-3,5-d iami η; 3'-Methyl-ö'-methyl-biph enyl-3,5-diami η.

Preferred are compounds of formula (I) in which (i) R1 is hydrogen or

(ii) R1 is hydrogen and at least 3 of the radicals R2 to R6 are hydrogen or

(iii) R1 is hydrogen, 3 of the radicals R2 to R6 are hydrogen and the two remaining radicals R2 to R6 independently represent hydrogen, fluorine, a methoxy group, a hydroxy group, a methyl group or an amino group.

Particularly preferred are the following [1,1'-biphenyl]-3,5-diamine derivatives of the formula (I): biphenyl-3,5-diamine; 4-benzo[1,3]dioxol-5-yl-

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benzene-1,3-diamine, 3\5'-diamino-biphenyl-4-ol; 4'-fluoro-biphenyl-3,5-diamine; 4'-amino-biphenyl-3,5-diamine; 3'-hydroxy-biphenyl-3,5-diamine; 4'-methoxy-biphenyl-3,5-diamine and their physiologically acceptable salts.

The compounds of formula (I) can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, such as hydrochloric acid, sulphuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.

The [1,1'-biphenyl]-3,5-diamine derivatives of the formula (I) are contained in the colorant according to the invention in a total amount of about 0.005 to 20 percent by weight, with an amount of about 0.01 to 5 percent by weight and in particular 0.1 to 2.5 percent by weight being preferred.

All developer substances known and suitable for such dyes can be used as developer substances, for example 1,4-diaminobenzene (p-phenylenediamine), 1,4-diamino-2-methylbenzene (p-toluenediamine), 1 ^-diamino^.e-dimethylbenzene, 1 ^-diamino-S.S-diethylbenzene, 1 ^-diamino-^.S-dimethylbenzene, 1 ,^-diamino^S-dimethylbenzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene, 1,4-diamino-2-(thiophen-3-yl)benzene, 1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl, 1 ^-ioiamino^-methoxymethylbenzene, 1,4-diamino-2-aminomethyl-benzene, i^-diamino^-hydroxymethyl-benzene, 1,4-diamino-2-(2-hydroxyethoxy)-benzene, 1-(2,5-diamino-phenyl)-ethanol, 2-(2-(acetylamino)ethoxy)-1,4-diamino-benzene, 4-phenylamino-aniline,

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4-Dimethylaminoaniline, 4-Diethylaminoaniline, 4-Dipropylaminoaniline, 4-[Ethyl(2-hydroxyethyl)amino]aniline, 4-[Di(2-hydroxyethyl)amino]aniline, 4-[Di (2-hydroxyethyl)amino]-2-methyl-aniline, 4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxypropyl)amino]-aniline, 4-[(2,3-dihydroxypropyl) amino]-aniline, 1,4-diamino-2-(2-hydroxyethyl)-benzene, 1,4-diamino-2-(i-methylethyl)-benzene, 1 ₎ 3-bis[(4-aminophenyl)(2 -hydroxyethyl)amino]-2-propanol, 1,4-ßis[(4-aminophenyl)amino]-butane, 1,8-Bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-amino-phenol, 4-amino-3-methyl-phenol, 4-amino-3-(hydroxymethyl)-phenol, 4-amino -3-fluoro-phenol, 4-methylamino-phenol, 4-amino-2-{aminomethyl)-;phenol, 4-amino-2-(hydroxymethyl)-phenol, 4-amino-2-fluoro-phenol, 4- Amino-2-[(2-hydroxyethyl)-amino]methylphenol, 4-amino-2-methyl-phenol, 4-amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol , 5-amino-salicylic acid, 2,5-diaminopyridine, 2,4,5,6-tetraamino-pyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone, 4,5-Diamino-1-(2-hydroxyethyl)-1H-pyrazole, 4,5-Diamino-1-(1-methylethyl)-1H-pyrazole, 4,5-Diamino-1-[(4-methylphenyl) methyl]-1H-pyrazole, 1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 4,5-diamino-3 -methyl-1-methyl-1 H-pyrazole, 4,5-diamino-3-methyl-1 -methyl-1 H-pyrazole, 2-amino-phenol, 2-amino-6-methyl-phenol and 2-amino -5-methyl-phenol can be used.

Furthermore, the colorant according to the invention can optionally additionally contain other known coupler substances, for example 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-(methyl-

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amino)-pyridine, 2 ₎ 6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1,3-diamino-benzene, 2,4-diamino-1-( 2-hydroxyethoxy)-benzene, 2,4-diamino-i,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diamino-benzene, 2-amino-1-(2 -hydroxyethoxy)-4-methylamino-benzene, 2,4-diaminophenoxy-acetic acid, 3-[di(2-hydroxyethyl)amino]-aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1 - ethoxybenzene, 5-methyl-2-(1methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline, 3-[(2-Aminoethyl)-amino]-aniline, 1,3-Di(2,4-diaminophenoxy)-propane, Di(2,4-diaminophenoxy)-methane, 1,S-Diamino^^-dimethoxy- benzene, 2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluoro- 2-methylphenol, 5-amino-4-methoxy-2-methyl-phenol, S-amino^-ethoxy^-methylphenol, S-amino^^-dichloro-phenol, ö-amino^^-dichloro-phenol, 3- Amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl)amino]-acetamide, 5-[(2-Hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-Hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)-amino]-phenol, 5-amino-2- ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol, 5-[(3-hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-dihydroxypropyl)amino]-2- methyl-phenol, 3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxy-pyridine, S-amino^-chloro^-methyl-phenol, 1-naphthol, 1,5-dihydroxy -naphthalene, 1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2,7-dihydroxy-naphthalene, 2-methyl-1-naphthol acetate, 1,3-dihydroxy-benzene, i-chloro^^-dihydroxy-benzene, 2-chloro-1,3-dihydroxy-benzene, 1^-dichloro-SS-dihydroxy^-methyl-benzene, 1,5-oichloro-2,4-dihydroxy-benzene, 1 ,S-DihydiOxy^-methyl-benzene, 3,4-methylenedioxyphenol, 3,4-methylendioxyaniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1 -hydroxy- S^-methylenedioxy-benzene, 3,4-Oiamino-benzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-

1,4(2H)-benzoxazine, S-methyl-i-phenyl-δ-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole,7 -Hydroxy-indole and 2,3-lndolindione.

The coupler substances and developer substances can be contained in the colorant according to the invention individually or in a mixture with one another, the total amount of coupler substances and developer substances in the colorant according to the invention (based on the total amount of the colorant) being in each case about 0.005 to 20 percent by weight, preferably about 0.01 to 5.0 percent by weight and in particular 0.1 to 2.5 percent by weight. The total amount of the developer substance-coupler substance combination contained in the colorant described here is preferably about 0.01 to 20 percent by weight, with an amount of about 0.02 to 10 percent by weight and in particular 0.2 to 6 percent by weight being particularly preferred. The developer substances and coupler substances are generally used in approximately equimolar amounts; However, it is not disadvantageous if the developing substances are present in a certain excess or deficiency (for example in a ratio (coupler: developer) of 1:2 to 1:0.5).

Furthermore, the colorant according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, as well as conventional anionic, cationic, zwitterionic or non-ionic direct dyes, for example triphenylmethane dyes such as ^^-aminophenylJ-i^imino^"^"-cyclohexadien-1"-ylidene)-methyl]-2-methylaminobenzene monohydrochloride

·

{CI 42 510) and 4-[(4 ^l amino-3'-methyl-phenyl)-(4"-imino-3"-methyl-2",5"cyclohexadien-1"-ylidene)-methyl]-2-methyl-aminobenzene monohydrochloride (Cl. 42 520), aromatic nitro dyes such as 4-(2'-hydroxyethyl)amino-nitrotoluene, 2-amino-4,6-dinitrophenol, 2-amino-5-(2'-hydroxyethyl)amino-nitrobenzene, 2-chloro-6-(ethylamino)-4-nitro-phenol, 4-chloro-N-(2-hydroxyethyl-2-nitroaniline, S-chloro^-hydroxy^-nitroaniline, 2-amino-4-chloro-6-nitrophenol and 1-[(2'-ureidoethyl)amino-4-nitrobenzene, azo dyes such as 6-[(4'-aminophenyl)azo]-5-hydroxy-naphthalene-1-sulfonic acid sodium salt (Cl. 14 805) and disperse dyes such as 1,4-tetraaminoanthraquinone and 1,4,5,8-tetraaminoanthraquinone. The above-mentioned color components and direct dyes can each be contained in the coloring agent according to the invention in an amount of about 0.1 to 4 percent by weight.

Of course, the coupler substances and developer substances as well as the other color components, if they are bases, can also be used in the form of physiologically acceptable salts with organic or inorganic acids, such as hydrochloric acid or sulfuric acid, or - if they have aromatic OH groups - in the form of salts with bases, for example as alkali phenolates.

In addition, if the dye according to the invention is to be used for dyeing hair, it may contain other additives customary in cosmetic products, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulphite, as well as perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care substances.

The preparation form of the colorant according to the invention can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution. The particularly preferred preparation forms, however, are a cream, a gel or an emulsion. Their composition represents a mixture of the dye components with the additives customary for such preparations.

Common additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerin or glycols such as 1,2-propylene glycol, as well as wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, oxyethylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkyl betaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides and oxyethylated fatty acid esters, as well as thickeners such as higher fatty alcohols, starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids, as well as care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The components mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 10 percent by weight.

The ready-to-use hair dye according to the invention is prepared by mixing the dye with an oxidizing agent immediately before use.

The oxidizing agents used are mainly hydrogen peroxide or its addition compounds with urea, melamine, sodium borate or sodium carbonate in the form of a 1 to 12 percent, preferably a 3 to 6 percent, aqueous solution. The weight ratio between hair dye and oxidizing agent is preferably about 5:1 to 1:3, in particular 1:1 to 1:2. Larger amounts of oxidizing agent are used primarily when the dye concentration in the hair dye is higher, or when the hair is to be bleached more strongly. In principle, however, it is also possible to use atmospheric oxygen to oxidize the dyes instead of the aforementioned oxidizing agents.

When the dye (whose pH is approximately 6 to 11.5) is mixed with the usually acidic oxidizing agent (whose pH is approximately 2 to 6.5), the pH of the ready-to-use hair dye according to the invention is adjusted to a pH value that is determined by the amount of alkali in the dye and the amount of acid in the oxidizing agent, as well as by the mixing ratio. Depending on the composition, the dye according to the invention can react in a slightly acidic, neutral or alkaline manner and, when ready for use, can have a pH of approximately 3 to 11.5, preferably approximately 6 to 10. The basic adjustment is preferably carried out with ammonia, although organic amines, for example 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, monoethanol-

amine and triethanolamine, or inorganic bases such as sodium hydroxide and potassium hydroxide can be used. Inorganic or organic acids, such as phosphoric acid, acetic acid, lactic acid, ascorbic acid, citric acid or tartaric acid, can be used to adjust the pH value in the acidic range.

Then, a sufficient amount of this mixture for the hair coloring treatment, depending on the thickness of the hair, generally about 60 to 200 grams, is applied to the hair and the mixture is left to act on the hair at about 15 to 25 degrees Celsius, preferably 30 to 40 degrees Celsius, for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, the hair is washed with a shampoo after this rinse and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.

The dye according to the invention containing [1,1'-biphenyl]-3,5-diamine derivatives of formula (I) as a coupler substance enables dyeing with excellent color fastness, particularly with regard to light fastness, wash fastness and rubbing fastness. In terms of coloring properties, the dye according to the invention offers a wide range of different color nuances depending on the type and composition of the color components, ranging from blonde to brown and violet to blue and black shades, with the achievable copper-colored and purple shades being particularly noteworthy. The shades are characterized by their particular color intensity. The very good coloring properties

of the dyeing agent according to the present application are further shown in the fact that this agent also enables, in particular, the dyeing of grey hair that has not been chemically damaged without any problems and with good coverage.

The preparation of the [1,1'-biphenyl]-3,5-diamine derivatives of the formula (J) according to the invention can be carried out using known synthesis methods, for example the methods described in the working examples.

The [1,1'-biphenyl]-3,5-diamine derivatives of the formula (I) are readily soluble in water and enable dyeings with high color intensity and excellent color fastness, particularly with regard to light fastness, wash fastness and rubbing fastness. They also have excellent storage stability, particularly as a component of the oxidation dyes described here.

Another object of the present invention are [λ,Γ-biphenyl]-3,5-diamine derivatives of the general formula (II),

R4

(II)

R1 is hydrogen, a halogen atom (fluorine, chlorine, bromine, iodine), a C^C^alkyl group, a C _r C ₄ -hydroxyalkoxy group, a C ₁ -C ₆ -alkyl group, a C^alkylthioether group, a trifluoromethane group, a -Si(CH ₃ ) ₃ group, a C 1 -C 4 -hydroxyalkyl group or a C ₂ -C ₄ dihydroxyalkyl group;

R2,R3,R4,R5,R6 can be the same or different and independently of one another represent hydrogen, a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, a hydroxy group, a C ₁ -C ₄ -alkoxy group, a C ₁ -C ₄ -hydroxyalkoxy group, a C _r C ₆ -alkyl group, a C ₁ -C ₄ -alkyl thioether group, a mercapto group, a nitro group, an amino group (NH2), a C^C^monoalkylamino group, a DKC^Ct-J-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^C^hydroxyalkyl group, a C ₂ -C ₄ dihydroxyalkyl group, a -CH=CHR7 group, a -(CH ₂ ) _P -CO ₂ R8 group or a -(CH ₂ ) _P -R9 group with p= 1,2,3 or 4, a -C(R10)=NR11 group or a C(R13)H-NR14R15 group, or two adjacent radicals R2 to R6 form an -O-CH2-O bridge; R7 is hydrogen, a nitro group, a CO ₂ R8 group or a -C(O)CH ₃ group;

R8, R10 and R13 may be the same or different and are independently hydrogen or a C^C^alkyl group; R9 is an amino group or a nitrile group; R11, R14 and Rt5 may be the same or different and are independently hydrogen, a hydroxy group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a Cj-C^-dihydroxyalkyl-

group or a residue of the formula ^=/;

• ft · · ·

R12 is hydrogen, an amino group or a hydroxy group; under the conditions that the compound of formula (II) has no inversion centre and at least one of the radicals R2 to R6 is not hydrogen and R4 is not a hydroxy group when the radicals R2, R3, R5 and R6 are hydrogen.

The following examples are intended to illustrate the subject matter of the invention in more detail without limiting it thereto.

Examples Example 1: Synthesis of [1,1 '-biphenyl]-3,5-diamines

A. Synthesis of (S-bromo-S-tert-butoxycarbonylamino-phenyl)-carbamic acid tert-butyl ester

A solution of 23.4 g (107 mmol) of di-tert-butyl dicarbonate in 30 ml of tetrahydrofuran is added dropwise to a solution of 8 g (42.8 mmol) of 5-bromo-1,3-phenylenediamine (prepared from 1-bromo-3,5-dinitrobenzene and subsequent reduction with Fe/HCl, EtOH analogously to the procedure from Synthesis 1978, 693 and Monatshefte Chem. 1968, 99, page 815) in 50 ml of dry tetrahydrofuran while heating to 70 ^° C. The reaction mixture is heated under reflux for 7 hours, then 4.6 g of di-tert-butyl dicarbonate are added and then heated under reflux again for 2 hours. The reaction mixture is then cooled to room temperature and concentrated. The solid residue is suspended in hexane, filtered and dried under high vacuum. 15 g (90% of theory) of (S-bromo-S-tert-butoxycarbonylaminophenyl)-carbamic acid tert-butyl ester are obtained.

¹ H-NMR (300MHz, CDCl ₃ ): δ= 7.36 (t, 1H); 7.26 (d, 2H); 6.44 (br.s, 2H); 1.50 (s, 18H).

B. Synthesis of [3-tert-butoxycarbonylamino-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-carbamic acid tert-butyl ester

A mixture of 5.5 g (14.2 mmol) of (S-bromo-S-tert-butoxycarbonylamino-phenyl)-carbamic acid tert-butyl ester from step A, 9 g (35.5 mmol) of 4 _> 4 _> 5,5,4',4 ^I ,5 ^I ,5 ^L -octamethyl-[2,2']bi[[1,3,2]dioxaborinanyl], 1.5 g (2.2 mmol) of dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (PdCl ₂ (dppf)) and 6.2 g (63.2 mmol) of potassium acetate are treated under argon with 210 ml of degassed dioxane. The mixture is stirred at 80 ^° C for 24 hours, then poured into water and extracted with ethyl acetate. The organic phase is then washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate and concentrated after filtration. The crude product obtained is purified on deactivated silica gel with a gradient of hexane (100%) over hexane/ethyl acetate (9:1 to 3:2). 4.70 g (77% of theory) of S-tert-butoxycarbonylamino-S-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-carbamic acid tert-butyl ester are obtained.

¹ H NMR (300MHz, CDCI ₃ ): S = 7.74 (t, 1 H); 7.55 (d, 2H); 6.45 (br.s, 2H); 1.50 (S, 18H); 1.31 (s.12H).

C. Synthesis of [1,1 '-biphenyl]-3,5-diamines

0.09 g (0.2 mmol) of 3-tert-butoxycarbonylamino-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-carbamic acid tert-butyl ester from step B and 0.4 mmol of the corresponding bromine derivative are dissolved in 10 ml of 1,2-dimethoxyethane under argon. Then 0.01 g (0.005

20

mmol) tetrakis-(triphenylphosphine)-palladium and 0.26 ml 2N potassium carbonate solution are added and the reaction mixture is heated to 80 ⁰ C. After the reaction is complete, the reaction mixture is poured into 10 ml ethyl acetate, the organic phase is extracted with dilute sodium hydroxide solution and then dried with magnesium sulfate. The solvent is distilled off on a rotary evaporator and the residue is purified on silica gel with petroleum ether/ethyl acetate (9:1). The product thus obtained is heated to 50 °C in 4 ml ethanol. Then 1.5 ml of a 2.9 molar ethanolic hydrochloric acid solution are added dropwise to prepare the hydrochloride. The precipitate is filtered off, washed twice with 1 ml ethanol and then dried.

a. Biphenyl-3,5,4'-triamine hydrochloride Bromine derivative used: 4-bromoaniline Mass spectrum: MH+ 200(100)

b. 3',5'-Diamino-biphenyl-4-ol hydrochloride Bromine derivative used: 4-bromo-phenol Mass η Spectrum: MH+ 201(100)

c. 4'-Methyl-biphenyl-3,5-diamine hydrochloride Bromine derivative used: 4-bromo-toluene Mass spectrum: MH+ 199(100)

d. 3',5'-Diamino-biphenyl-4-carbonitrile hydrochloride Bromine derivative used: 4-bromo-benzonitrile Mass spectrum: MH+ 210(100)

e. 4'-Nitro-biphenyl-3,5-diamine hydrochloride Bromine derivative used: 4-bromo-nitro-benzene Mass spectrum: MH+ 230(100)

21

f. 4'-Trifluoromethyl-biphenyl-3,5-diamine hydrochloride Bromine derivative used: 4-bromo-trifluorotoluene Mass spectrum: MH+ 253(100)

g. 5-Benzo[1,3]dioxol-5-yl-benzene-1,3-diamine hydrochloride Bromine derivative used : 5-Bromo-benzo[1,3]dioxole Mass spectrum: MH+ 229(100)

h. 4'-Fluoro-biphenyl-3,5-diamine hydrochloride Bromine derivative used: 4-bromo-fluorobenzene Mass spectrum: MH+ 203(100)

i. 2',4'-Dimethyl-biphenyl-3,5-diamine hydrochloride Bromine derivative used: 2-bromo-m-xylene Mass spectrum: MH+ 213(100)

j. 3',5'-Diamino-biphenyl-3-ol hydrochloride Bromine derivative used: 3-bromo-phenol Mass spectrum: MH+ 201(100)

k. 1 -(3',5'-Diamino-biphenyl-3-yl)-ethanone hydrochloride Bromine derivative used: 3-bromo-acetophenone Mass spectrum: MH+ 227(100)

I. 2'-Nitro-biphenyl-3,5-diamine hydrochloride

Bromine derivative used: 2-bromo-nitrobenzene Mass spectrum: MH+ 230(100) &tgr;&eegr;. 3'-Methoxy-biphenyl-3,5-diamine hydrochloride Bromine derivative used: 3-bromo-anisole Mass spectrum: MH+ 215(100)

n. 4'-Methylsulfanyl-biphenyl-3,5-diamine hydrochloride Bromine derivative used: 1-bromo-4-methylsulfanyl-benzene Mass spectrum: MH+ 231(100)

&ogr;. 2'-Chloro-4'-nitro-biphenyl-3,5-diamine hydrochloride Bromine derivative used : Bromo-2-chloro-4-nitro-benzene Mass spectrum: MH+ 264(100)

Examples 2 to 16: Hair dye

Hair dye solutions of the following composition are produced:

1.25 mmol coupler substance of formula (I) according to Table

1.25 mmol developer substance according to Table 1

1.0 g potassium oleate (8% aqueous solution)

1.0 g ammonia (22% aqueous solution)

1.0 g ethanol

0.3 g ascorbic acid

ad 100.0 g water

Immediately before use, 50 g of the above dye solution are mixed with 50 g of a 6% aqueous hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 ⁰ C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 1.

Table 1 ■ I.
1,4-Di-
amino
benzene Coupler substance III.
I
2,5-Diamino-
phenyl
ethanol
su If at IV.
4,5-Diamino-
hydroxy-
ethyl)-
pyrazole-
sulfate Matchmaker copper II.
2,5-Diamino-
toluene sulfate copper purple Example substance
the formula
(I) copper copper copper violet No. according to
Example 1a copper copper copper \ violet 2. according to
Example 1b brown copper reddish brown light purple 3. according to
Example 1c brown brown reddish brown light purple 4. according to
Example 1d brown brown reddish brown light purple 5. according to
Example 1e copper brown copper violet 6. according to i
Example If copper copper copper violet 7. according to
Example 1g brown copper '. reddish brown violet 8th. according to
Example 1 h brown 9. according to
Example 1i 10.

· ■··

11. according to
Example 1j brown brown reddish brown violet 12. according to
Example 1k reddish brown reddish brown reddish brown light purple i 13. according to
Example 11 brown brown brown light purple 14. according to
Example 1m brown reddish brown reddish brown violet 15. according to
Example 1n brown bcaun reddish brown light purple 16. according to
Example 1o brown brown reddish brown light purple

Examples 17 to 38: Hair dye

Hair dye solutions of the following composition are produced:

Ug

Yg 10.0 g 10.0 g 10.0 g 0.3 g

to 100.0 g

[1,1'-Biphenyl-3,5-diamine of formula (I) (Coupling substance Kt or K2 according to Table 3) Developer substance E8 to E15 according to Table Coupler substance K12 to K36 according to Table Potassium oleate (8% aqueous solution) Ammonia (22% aqueous solution) Ethanol Ascorbic acid Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6% aqueous hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 ⁰ C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The dyeing results are summarized in Table 4.

Examples 39 to 51: Hair dyes

Cream-like color carrier masses of the following composition are produced:

Xg [1,1 '-Biphenyl]-3,5-diamine of the formula (I)

(Coupler substance K1 or K2 according to Table 3) U g developer substance E8 to E15 according to Table 2 Y g coupler substance K12 to K36 according to Table 3 Z g e-chloro^-ethylamino^-nitro-phenol (D2) 15.0 g cetyl alcohol
0.3 g ascorbic acid
3.5 g sodium lauryl alcohol diglycol ether sulfate, 28 percent

aqueous solution

3.0 g ammonia, 22% aqueous solution 0.3 g sodium sulphite, anhydrous ad 100 g water

30 g of the above colouring cream are mixed with 30 g of a 6% hydrogen peroxide solution immediately before use

ti

mixed. The mixture is then applied to the hair. After a contact time of 30 minutes at 40 ⁰ C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The dyeing results are summarized in Table 5.

Table 2: Developer substances E8 1,4-Diaminobenzene E9 1,4-Diamino-2-(2-hydroxyethyl)-benzene sulfate E10 3-methyl-4-aminophenol E11 4-Amino-2-aminomethylphenol dihydrochloride Egg 2 4-Aminophenol E13 N,N-Bis(2'-hydroxyethyl)-p-phenylenediamine sulfate E14 4,5-Diamino-1-(2'-hydroxyethyl)-pyrazole sulfate E15 2,5-Diaminotoluene sulfate

Table 3: Couplers &Kgr;1 Biphenyl-3,5,4'-triamine hydrochloride &Kgr;2 S'.S'-Diamino-biphenyl^-ol hydrochloride &Kgr;12 2-Amino-4-(2 '-hydroxyethyl)amino-anisole sulfate &Kgr;13 1,3-Oiamino-4-(2'-hydroxyethoxy)benzene sulfate &Kgr;21 3-Aminophenol &Kgr;22 5-Amino-2-methylphenol &Kgr;23 S-Amfno^-chloro-e-methyl-phenol &Kgr;24 5-Amino-4-fluoro-2-methyl-phenol-sweet fat &Kgr;25 1-Naphthol &Kgr;26 1 -Acetoxy-2-methyl-naphthalene &Kgr;31 1,3-Dihydroxybenzene &Kgr;32 2-Methyl-1,3-dihydroxy-benzene, &Kgr;33 1-Chloro-2,4-dihydroxybenzene &Kgr;34 4-(2'-Hydroxyethyl)amino-1,2-methylenedioxybenzene;
hydrochlorid &Kgr;35 3,4-methylenedioxyphenol &Kgr;36 2-Amino-5-methyl-phenol j

Table 4: Hair dyes

Example No. 17 18 19 20 0.20 0.15 0.25 0.20 Dyes (Amount of dye in grams) K1 0.25 0.30 E8 0.20 0.20 E9 E15 0.08 0.10 0.12 K31 0.10 K32 reddish brown reddish brown reddish brown; reddish brown K33 Dyeing result

29

Table 4 (continued )

Example No. 21 22 23 24 0.15 0.10 0.20 0.10 Dyes (Amount of dye in grams) K1 0.25 0.30 EB 0.20 0.20 E9 E15 0.30 0.30 EIO 0.30 E11 0.30 E12 E14 0.10 0.20 0.10 K31 0.12 K32 0.30 0.30 0.30 K33 0.35 K25 reddish brown reddish brown reddish brown reddish brown K26 Dyeing result

·· · · • · • · • * · • ·
• ·
· ■ · •
• · · ■ · · · · · » · · · · ·
· •
• · ·

30

Table 4 (continued )

Example No. 25 26 27 28 0.20 0.15 0.25 0.20 Dyes (Amount of dye in grams) K2 0.25 0.30 £8 0.20 0.20 E9 E15 0.08 0.10 0.12i K31 0.10 K32 reddish brown reddish brown reddish brown reddish brown K33 Dyeing result

31

Table 5 (Continuation)

Example No. 29 30 31 32 0.15 0.10i 0.20 0.10 &iacgr; 0.20 Dyes (Amount of dye in grams) K2 0.25 0.30 E8 0.20 E9 0.30 E15 0.30i 0.30 0.20 ; E10 0.30 ^: E11 E12 0.30 E14 0.10 0.10 reddish brown K31 0.12 K32 0.30 0.30 K33 0.35 K25 reddish brown reddish brown reddish brown K26 Staining result &iacgr;

32

Table 4 (continued )

Example No. 33 34 35 36 37 38 (Amount of dye in grams) 0.25 0.20 0.23 0.10 0.10 0.20 Dyes K2 0.30 0.25 0.30 E8 0.25 0.30 0.25 E9 E15 0.10 0.10 0.10 0.12 0.05 0.05 K12 0.10 0.10 0.05 K13 0.10 0.10 K31 K32 0.05 K33 0.05 K21 0.05 0.10i 0.10 0.10 K22 blond blond blond blond blond blond K23 Dyeing result

33

Table 5: Hair dyes

Example No. 39 40 41 42 43 45 (Amount of dye in grams) 0.60 1.30 1.15 0.40 0.20 0.25 Dyes Kt 1.50 1.60 0.70 E8 1.80 0.70 0.70 E13 E15 1.20 1.30 1.15 0.15 0.15 0.15 0.50 0.20 0.20 K12 K31 0.10 0.10 0.10 0.05i 0.10 0.10 ; 0.10 D2 black black black brown brown brown K23 Dyeing result

·

·

Table 5: (For setting) 47 48 49 50 51 (Amount of dye in grams) 1.30 0.50 0.45 0.20 0.40 0.40 46 Example No. 1.50 Dyes 1.60 0.70 K2 1.80 0.70 0.70 E8 1.20 1.30 1.15 0.15 0.15 0.15 E13 0.50 0.70 0.20 E15 0.10 0.10 0.10 K12 0.05 0.10 0.10 0.10 K31 black black black brown brown brown D2 K23 Dyeing result

All percentages contained in this application are by weight unless otherwise stated.

• · · ·♦·♦

Claims (13)

1. Agent for the oxidative coloration of keratin fibers based on a developer substance-coupler substance combination, characterized in that it contains as coupler substance at least one [1,1'-biphenyl]-3,5-diamine derivative of the formula (I) or its salt with an inorganic or organic acid,


wherein
R1 is hydrogen, a halogen atom, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ hydroxyalkoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ alkylthioether group, a trifluoromethane group, a -Si(CH ₃ ) ₃ group, a C ₁ -C ₄ hydroxyalkyl group or a C ₂ -C ₄ dihydroxyalkyl group;
R2, R3, R4, R5, R6 can be the same or different and independently of one another represent hydrogen, a halogen atom, a cyano group, a hydroxy group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ hydroxyalkoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ alkyl thioether group, a mercapto group, a nitro group, an amino group (NH2), a C ₁ -C ₄ monoalkylamino group, a di(C ₁ -C ₄ ) 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 -C ₄ hydroxyalkyl group, a C ₂ -C ₄ dihydroxyalkyl group, a -CH=CHR7 group, a -(CH ₂ ) _p -CO ₂ R8 group or a -(CH ₂ ) _p -R9 group with p = 1, 2, 3 or 4, a -C(R10)=NR11 group or a C(R13)H-NR14R15 group, or two adjacent radicals R2 to R6 form an -O-CH ₂ -O bridge;
R7 is hydrogen, a nitro group, a CO ₂ R8 group or a -C(O)CH ₃ group;
R8, R10 and R13 may be the same or different and are independently hydrogen or a C ₁ -C ₄ alkyl group;
R9 is an amino group or a nitrile group;
R11, R14 and R15 may be the same or different and independently of one another are hydrogen, a hydroxy group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₂ -C ₄ dihydroxyalkyl group or a radical of the formula


are;
R12 is hydrogen, an amino group or a hydroxy group; with the proviso that the compound of formula (I) does not have an inversion centre. 2. Agent according to claim 1, characterized in that R1 is hydrogen. 3. Agent according to claim 1 or 2, characterized in that R1 is hydrogen and at least 3 of the radicals R2 to R6 are hydrogen. 4. Agent according to one of claims 1 to 3, characterized in that R1 is hydrogen, 3 of the radicals R2 to R6 are hydrogen and the two remaining radicals R2 to R6 independently represent hydrogen, fluorine, a methoxy group, a hydroxy group, a methyl group or an amino group. 5. Agent according to one of claims 1 to 4, characterized in that the [1,1'-biphenyl]-3,5-diamine derivative of the formula (I) is selected from biphenyl-3,5-diamine; 4-benzo[1,3]dioxol-5-yl-benzene-1,3-diamine; 3',5'-diamino-biphenyl-4-ol; 4'-fluoro-biphenyl-3,5-diamine; 4'-aminobiphenyl-3,5-diamine; 3'-hydroxy-biphenyl-3,5-diamine; 4'-methoxybiphenyl-3,5-diamine and their physiologically acceptable salts. 6. Agent according to one of claims 1 to 5, characterized in that the [1,1'-biphenyl]-3,5-diamine of the formula (I) is contained in an amount of 0.005 to 20 percent by weight. 7. Agent according to one of claims 1 to 6, characterized in that the developer substance is selected from the group consisting of 1,4-diaminobenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene, 1,4-diamino-2-(thiophen-3-yl)benzene, 1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diamino-biphenyl, 1,4-diamino-2-methoxymethylbenzene, 1,4-diamino-2-aminomethyl-benzene, 1,4-diamino-2-hydroxymethyl-benzene, 1,4-diamino-2-(2-hydroxyethoxy)-benzene, 1-(2,5-diamino-phenyl)-ethanol, 2-(2-(acetylamino)ethoxy)-1,4-diamino-benzene, 4-phenylamino-aniline, Dimethylamino-aniline, 4-diethylamino-aniline, 4-dipropylamino-aniline, 4-[ethyl(2-hydroxyethyl)amino]-aniline, 4-[di(2-hydroxyethyl)amino]-aniline, 4-[di(2-hydroxyethyl)amino]-2-methyl-aniline, 4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxypropyl) amino]-aniline, 4-[(2,3-dihydroxypropyl)amino]-aniline, 1,4-Diamino-2-(2-hydroxyethyl)-benzene, 1,4-Diamino-2-(1-methyl-ethyl)-benzene, 1,3-Bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol, 1,4-Bis[(4-Aminophenyl)amino]-butane, 1,8-Bis(2,5-diaminophenoxy)-3,6-diox aoctane, 4-amino-phenol, 4-amino-3-methyl-phenol, 4-amino-3-(hydroxymethyl)-phenol, 4-amino-3-fluoro-phenol, 4-methylamino-phenol, 4-amino-2-(aminomethyl)-phenol, 4-amino-2-(hydroxymethyl)-phenol, 4-amino-2-fluoro-phenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl - phenol, 4-amino-2-methyl-phenol, 4-Amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol, 5-amino-salicylic acid, 2,5-diaminopyridine, 2,4,5,6-tetraamino-pyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone, 4,5-diamino-1-(2-hydroxyethyl)-1H-pyr azole, 4,5-diamino-1-(1-methyl-ethyl)-1H-pyrazole, 4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole, 1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole, 4,5-diamino-1-methyl-1H-pyrazole, 1H-pyrazole, 4,5-diamino-3-methyl-1-methyl-1H-pyrazole, 2-amino-phenol, 2-amino-6-methyl-phenol and 2-amino-5-methyl-phenol. 8. Agent according to one of claims 1 to 7, characterized in that it additionally contains at least one further coupler substance and/or at least one direct dye. 9. Agent according to one of claims 1 to 8, characterized in that the developer substances and additional coupler substances, based on the total amount of the colorant, are each contained in a total amount of 0.005 to 20 percent by weight. 10. Agent according to one of claims 1 to 9, characterized in that it is mixed with the oxidizing agent in a weight ratio of 5:1 to 1:3 before use. 11. Agent according to claim 10, characterized in that the ready-to-use oxidation dye has a pH value of 3 to 11.5. 12. Agent according to one of claims 1 to 11, characterized in that it is a hair dye. 13. [1,1'-Biphenyl]-3,5-diamine derivatives of the general formula (II),


wherein
R1 is hydrogen, a halogen atom, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ hydroxyalkoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ alkylthioether group, a trifluoromethane group, a -Si(CH ₃ ) ₃ group, a C ₁ -C ₄ hydroxyalkyl group or a C ₂ -C ₄ dihydroxyalkyl group;
R2, R3, R4, R5, R6 can be the same or different and independently of one another are hydrogen, a halogen atom, a cyano group, a hydroxy group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ hydroxyalkoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ alkylthioether group, a mercapto group, a nitro group, an amino group (NH ₂ ), a C ₁ -C ₄ monoalkylamino group, a di(C ₁ -C ₄ ) 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 -C ₄ hydroxyalkyl group, a C ₂ -C ₄ dihydroxyalkyl group, a -CH=CHR7 group, a -(CH ₂ ) _p -CO ₂ R8 group or a -(CH ₂ ) _p -R9 group with p = 1, 2, 3 or 4, a -C(R10)=NR11 group or a C(R13)H-NR14R15 group, or two adjacent radicals R2 to R6 form an -O-CH ₂ -O bridge;
R7 is hydrogen, a nitro group, a CO ₂ R8 group or a -C(O)CH ₃ group;
R8, R10 and R13 may be the same or different and independently represent hydrogen or a C ₁ -C ₄ alkyl group;
R9 is an amino group or a nitrile group;
R11, R14 and R15 may be the same or different and independently of one another are hydrogen, a hydroxy group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₂ -C ₄ dihydroxyalkyl group or a radical of the formula


are;
R12 is hydrogen, an amino group or a hydroxy group;
under the conditions that this compound of formula (II) has no inversion center, and at least one of the radicals R2 to R6 is not hydrogen and R4 is not a hydroxy group, if R2=R3=R5=R6=hydrogen.