3-(2,5-diaminophenyl)-acrylamide derivatives and coloring agents containing said compounds

The invention relates to novel 3-(2,5-diaminophenyl)acrylamide derivatives and to dyeing agents for keratin fibers containing these compounds.

In the area of keratin fiber dyeing, particularly hair dyeing, oxidation dyes have attained substantial importance. In this case, the coloration is produced by reaction of certain developers with certain couplers in the presence of an appropriate oxidant. Suitable developers are, in particular, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, p-aminophenol, 1,4-diaminobenzene and 4,5-diamino-1-(2-hydroxyethyl)pyrazole, and suitable couplers are, for example, resorcinol, 2-methylresorcinol, 1-naphthol, 3-aminophenol, m-phenylenediamine, 2-amino-4-(2′-hydroxyethyl)aminoanisole, 1,3-diamino-4-(2′-hydroxyethoxy)benzene and 2,4-diamino-5-fluorotoluene.

To cover the important blond range, direct aromatic nitro dyes, in particular, were heretofore added to the oxidative hair colorants.

The use of substituted p-phenylenediamines as dye components in oxidative hair colorants is known from the literature, for example from German Unexamined Patent Application DE 198 22 041, Unexamined European Patent Applications EP 0 634 163 and EP 0 819 424, German Unexamined Patent Application 39 17 304 and European Unexamined Patent Application 0 007 537. These compounds, however, do not meet the requirements placed on dyes for oxidative colorants for the blond range in all respects. Hence, the need for suitable novel dyes continued to exist.

We have now found; that certain p-phenylenediamine derivatives together with the usual couplers make it possible to achieve an intense blond coloration of fibers, particularly keratin fibers, for example hair. By use of these p-phenylenediamine derivatives in an oxidizing medium, intense color shades are thus obtained which are unusually light-fast and wash-fast.

Hence, the object of the present invention are 3-(2,5-diaminophenyl)acrylamide derivatives of general formula (I) or their physiologically tolerated, water-soluble salts

wherein

R1, R2, R3 and R4 can be equal or different and independently of each other denote hydrogen, a C 1 -C 6 -alkyl group, a C 2 -C 4 -hydroxyalkyl group or a C 3 -C 4 -dihydroxyalkyl group or R1 and R2 or R3 and R4 form a four-membered to eight-membered aliphatic ring and at least two of the R1 to R4 groups denote hydrogen;

R5 denotes hydrogen, a halogen atom (F, Cl, Br, I), a C 1 -C 4 -alkyl group, a C 1 -C 4 -hydroxyalkyl group or a C 1 -C 4 -alkoxy group;

R6 and R7 can be equal or different and independently of each other denote hydrogen, a C 1 -C 2 -alkoxy, C 1 -C 6 -alkyl, unsaturated C 3 -C 6 -alkyl, C 2 -C 4 -hydroxyalkyl, C 3 -C 4 -dihydroxyalkyl, C 2 -C 4 -aminoalkyl, C 2 -C 4 -dimethylaminoalkyl, C 2 -C 4 -acetylaminoalkyl, C 2 -C 4 -methoxyalkyl, C 2 -C 4 -ethoxyalkyl, C 1 -C 4 -cyanoalkyl, C 1 -C 4 -carboxyalkyl, C 2 -C 4 -aminocarbonylalkyl group, a pyridylmethyl, furfuryl, hydrogenated furfuryl, substituted pyridyl group, a group of formula (II)

a group of formula (III)

or a group of formula (IV)

or R6 and R7 form a ring of formula

R8, R9 and R21 can be equal or different and independently of each other denote hydrogen or a C 1 -C 6 -alkyl group;

R10 denotes hydrogen, a carboxy group or an aminocarbonyl group;

R11 and R12 can be equal or different and independently of each other denote hydrogen, a hydroxyl, aminocarbonyl, methylthiomethyl group, a phenyl- or hydroxyl-substituted phenyl group or a group of formula

R13, R14, R15, R16 and R17 can be equal or different and independently of each other denote hydrogen. a halogen atom (F, Cl, Br, I), a cyano group, a hydroxyl, C 1 -C 4 -alkoxy, C 1 -C 4 -hydroxyalkoxy, C 1 -C 6 -alkyl, C 1 -C 4 -alkyl thioether, mercapto, nitro, amino, alkylamino, hydroxyalkylamino, dialkylamino, di(hydroxyalkyl)amino, (dihydroxyalkyl)amino, (hydroxyalkyl)alkylamino, trifluoromethane, —C(O)H, —C(O)CH 3 , —C(O)CF 3 , —Si(CH 3 ) 3 , C 1 -C 4 -hydroxyalkyl or C 2 -C 4 -dihydroxyalkyl group or two adjacent R13 to R17 groups together form an —O—CH 2 —O— bridge;

R18 denotes a C 1 -C 4 -alkyl, benzyl or C 1 -C 4 -hydroxyalkyl group;

R19 denotes hydrogen or a C 1 -C 6 -alkyl group, and

R20 denotes hydrogen, a hydroxyl, carboxy, aminocarbonyl or hydroxymethyl group.

Noteworthy among compounds of formula (I) are, for example:

3-(2,5-diaminophenyl)-N-methylacrylamide, 3-(2,5-diaminophenyl)-N-propylacrylamide, 3-(2,5-diaminophenyl)-1-morpholin-4-ylpropenone, 3-(2,5-diaminophenyl)-N-(1-hydroxymethylpropyl)acrylamide, 3-(2,5-diaminophenyl)-N-furan-2-ylmethylacrylamide, 3-(2,5-diaminophenyl)-N-methoxy-N-methylacrylamide, 3-(2,5-diaminophenyl)-N-(2-hydroxy-1-methylethyl)acrylamide, N-(2-aminoethyl)-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-(tetrahydrofuran-2-ylmethyl)acrylamide, N-cyclopropyl-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-isopropylacrylamide, 3-(2,5-diaminophenyl)-N-(2-methoxyethyl)acrylamide, 3-(2,5-diaminophenyl)-1-(4-hydroxypiperidin-1-yl)propenone, N-(2-acetylaminoethyl)-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-(2-morpholin-4-ylethyl)acrylamide, 3-(2,5-diaminophenyl)-N-[3-(2-ketopyrrolidin-1-yl)propyl]acrylamide, 2-[3-(2,5-diaminophenyl)acryloylamino]-3-methylbutyric acid, [3-(2,5-diaminophenyl)acryloylamino]acetic acid, N-allyl-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-[2-(5-nitropyridin-2-ylamino)ethyl]acrylamide, 3-(2,5-diaminophenyl)-N-(3-imidazol-1-ylpropyl)acrylamide, 3-(2,5-diaminophenyl)-N-[2-(3H-imidazol-4-yl)ethyl]acrylamide, N-(4-aminophenyl)-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-[2-(4-sulfamoylphenyl)ethyl]acrylamide, N-[5-chloro-4-(2-hydroxyethylamino)-2-nitrophenyl]-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-1-pyrrolidin-1-ylpropenone, 3-(2,5-diaminophenyl)-N-pyridin-2-ylacrylamide, N-[3-(2,5-diaminophenyl)-2-propenoyl]-L-glutamic acid trifluoroacetate, N2-[3-(2,5-diaminophenyl)-2-propenoyl]-glutamine trifluoroacetate, N-[4-amino-2-(2-hydroxyethyl)-2H-pyrazol-3-yl]-3-(2,5-diaminophenyl)acrylamide, N-(4-amino-2(3)-methylphenyl)-3-(2,5-diaminophenyl)acrylamide, N-[4-amino-2(3)-(2-hydroxyethyl)phenyl]-3-(2,5-diaminophenyl)acrylamide, N-{4-[bis-(2-hydroxyethyl)amino]phenyl}-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-(4-hydroxyphenyl)acrylamide, 3-(2,5-diaminophenyl)-N-(3-hydroxy-4-methylphenyl)acrylamide, N-(3-aminophenyl)-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-(3-hydroxy-5-hydroxymethyl-2-methyl-4-pyridinylmethyl)acrylamide, 3-(2,5-diaminophenyl)-N-(2-hydroxy-5-nitrophenyl)acrylamide, N-(3-chloro-2-hydroxy-5-nitrophenyl)-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-di-aminophenyl)-1-(2-hydroxymethyl-1-pyrrolidinyl)propenone, 3-(2,5-diaminophenyl-1-(3-hydroxy-1-pyrrolidinyl)propenone, 1-[3-(2,5-diaminophenyl)acryloyl]pyrrolidine-2-carboxamide, 3-(2,5-diaminophenyl)-1-(3-hydroxy-1-piperidinyl)propenone, 3-(2,5-diaminophenyl)-N-(2-hydroxy-1-hydroxymethylethyl)acrylamide, N-(1-carbamoyl-2-hydroxyethyl)-3-(2,5-diaminophenyl)acrylamide, N-[3-(2,5-diaminophenyl)-2-propenoyl]-L-aspartic acid, N2-[3-(2,5-diaminophenyl)-2-propenoyl]-L-asparagine, N-[3-(2,5-diaminophenyl)-2-propenoyl]-L-leucine, N-[5-amino-2(4)-2-hydroxyethoxy)phenyl]-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-ethylacrylamide, N-benzo[1,3]dioxol-5-yl-3-(2,5-diaminophenyl)acrylamide, 2-[3-(2,5-diaminophenyl)acryloylamino]-4-methylpentanoic acid, 3-(2,5-diaminophenyl)-1-(6,7-dihydroxy-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl)propenone, N-(4-aminophenyl)-3-(N 2 ,N 2 -bis-methyl-2,5-diaminophenyl)acrylamide, N-(4-aminophenyl)-3-(N 5 ,N 5 -bis-methyl-2,5-diaminophenyl)acrylamide, N-(4-aminophenyl)-3-[N 2 ,N 2 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]acrylamide, N-(4-aminophenyl)-3-[N 5 ,N 5 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]acrylamide, N-(4-aminophenyl)-3-[N 2 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]acrylamide, N-(4-aminophenyl)-3-[N 5 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]acrylamide, N-(4-aminophenyl)-3-[2-(1-pyrrolidinyl)-5-aminophenyl]acrylamide, N-(4-aminophenyl)-3-[5-(1-pyrrolidinyl)-2-aminophenyl]acrylamide, 3-N 2 ,N 2 -bis-methyl-2,5-diaminophenyl-N-ethylacrylamide, 3-[N 5 ,N 5 -bis-methyl-2,5-diaminophenyl]-N-ethylacrylamide, 3-[N 2 ,N 2 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]-N-ethylacrylamide, 3-[N 5 ,N 5 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]-N-ethylacrylamide, 3-[N 2 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]-N-ethylacrylamide, 3-[N 5 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]-N-ethylacrylamide, 3-[2-(1-pyrrolidinyl)-5-aminophenyl]-N-ethylacrylamide, 3-[5-(1-pyrrolidinyl)-2-aminophenyl]-N-ethylacrylamide, 3-(N 2 ,N 2 -bis-methyl-2,5-diaminophenyl)-N-propylacrylamide, 3-(N 5 ,N 5 -bis-methyl-2,5-diaminophenyl)-N-propylacrylamide, 3-[N 2 ,N 2 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]-N-propylacrylamide, 3-[N 5 ,N 5 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]-N-propylacrylamide, 3-[N 2 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]-N-propylacrylamide, 3-[N 5 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]-N-propylacrylamide, 3-[2-(1-pyrrolidinyl)-5-aminophenyl]-N-propylacrylamide, 3-[5-(1-pyrrolidinyl)-2-aminophenyl]-N-propylacrylamide, 3-(N 2 ,N 2 -bis-methyl-2,5-diaminophenyl)-N-(2-hydroxy-1-methylethyl)acrylamide, 3-(N 5 ,N 5 -bis-methyl-2,5-diaminophenyl)-N-(2-hydroxy-1-methylethyl)acrylamide, 3-[N 2 ,N 2 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]-N-(2-hydroxy-1-methylethyl)acrylamide, 3-[N 5 ,N 5 -bis-(2-hydroxyethyl)-2,5-diaminophenyl]-N-(2-hydroxy-1-methylethyl)acrylamide, 3-[N 2 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]-N-(2-hydroxy-1-methylethyl)acrylamide, 3-[N 5 -(2,3-dihydroxypropyl)-2,5-diaminophenyl]-N-(2-hydroxy-1-methylethyl)acrylamide, 3-[2-(1-pyrrolidinyl)-5-aminophenyl]-N-(2-hydroxy-1-methylethyl)acrylamide, 3-[5-(1-pyrrolidinyl)-2-aminophenyl]-N-(2-hydroxy-1-methylethyl)acrylamide or the physiologically tolerated salts thereof.

Preferred compounds of formula (I) are those wherein (i) one or more of the R5, R8 and R9 groups denote hydrogen and/or (ii) R1, R2, R3 and R4 denote hydrogen and/or (iii) R6 denotes a methyl group, a methoxy group or a C 2 -C 4 hydroxyalkyl group and R7 denotes a C 2 -C 4 -hydroxyalkyl group and/or (iv) R6 denotes hydrogen and R7 denotes a C 1 -C 6 -alkyl group, an unsaturated C 3 -C 6 -alkyl group, a C 2 -C 4 -hydroxyalkyl group, a furfuryl group, a substituted phenyl group or a substituted pyrazoyl group, and/or (v) R6 and R7 form an aliphatic ring of formula

In particular, the following compounds are noteworthy:

3-(2,5-diaminophenyl)-N-propylacrylamide, 3-(2,5-diaminophenyl)-N-2-furanylmethylacrylamide, 3-(2,5-diaminophenyl)-N-methoxy-N-methylacrylamide, 3-(2,5-diaminophenyl)-N-(2-hydroxy-1-methylethyl)acrylamide, N-cyclopropyl-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-isopropylacrylamide, N-(4-aminophenyl)-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-1-pyrrolidin-1-ylpropenone, N-[4-amino-2-(2-hydroxyethyl)-2H-pyrazol-3-yl]-3-(2,5-diaminophenyl)acrylamide, N-(4-amino-2(3)-methylphenyl)-3-(2,5-diaminophenyl)acrylamide, N-{4-[bis-(2-hydroxyethyl)amino]phenyl}-3-(2,5-diaminophenyl)acrylamide, 3-(2,5-diaminophenyl)-N-(4-hydroxyphenyl)acrylamide, 3-(2,5-diaminophenyl)-1-(3-hydroxypyrrolidin-1-yl)propenone, N-[5-amino-2(4)-2-(hydroxyethoxy)phenyl]-3-(2,5-diaminophenyl)acrylamide and 3-(2,5-diaminophenyl)-N-ethylacrylamide.

The 3-(2,5-diaminophenyl)acrylamide derivatives of formula (I) can be used as the free bases as well as in the form of their physiologically tolerated salts with inorganic or organic acids, for example hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.

The 3-(2,5-diaminophenyl)acrylamide derivatives of formula (I) of the invention can be prepared by known methods of synthesis. For example, the synthesis of the compound of the invention can be carried out as follows:

By aminolysis of a substituted benzene of formula (Ia)

wherein Ra denotes an appropriate protective group, for example a group as described in Organic Synthesis, Chapter 7, “Protection for the Amino Group”, page 309 ff, Wiley Interscience, 1991; Rb stands for NR1Ra or NR3R4 and R22 denotes a carboxylic acid group, a carboxylic acid chloride group, a carboxylate ester group of a carboxylic anhydride group,

with an amine having formula NHR6R7,

wherein R1, R3, R4, R5, R6, R7, R8 and R9 have the same meaning as in formula (I), followed by elimination of the protective group.

The 3-(2,5-diaminophenyl)acrylamide derivatives of formula (I) of the invention are readily water-soluble and give colorations of high intensity and excellent color stability, particularly in terms of light fastness, wash fastness and rubbing fastness.

Another object of the present invention are therefore agents for oxidative dyeing of keratin fibers, for example hair, furs, feathers or wool, particularly human hair, said agents being based on a developer-coupler combination which as developer contains at least one 3-(2,5-diaminophenyl)acrylamide derivative of formula (I).

The 3-(2,5-diaminophenyl)acrylamide derivative of formula (I) is contained in the colorant of the invention in an amount from about 0.005 to 20 wt. %, an amount from about 0.01 to 5 wt. % and particularly from 0.1 to 2.5 wt. % being preferred.

Preferred coupler compounds are N-(3-dimethyl-aminophenyl)urea, 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-hydroxyethylamino]-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-diamino-benzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene, 1,3-diamino-4-(2,3-dihydroxypropoxy)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-diamino-phenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]-aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxy-ethyl)amino]-aniline, 3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)-propane, di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene, 2,6-bis(2-hydroxyethyl)aminotoluene, 4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methyl-phenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2-[(3-hydroxyphenyl)amino]acetamide, 5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol, 5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-[(2-hydroxy-ethyl)amino]phenol, 3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethylphenol, 5-amino-2-methoxyphenol, 2-(4-amino-2-hydroxyphenoxy)ethanol, 5-[(3-hydroxypropyl)amino]-2-methylphenol, 3-[(2,3-dihydroxypropyl)amino]-2-methylphenol, 3-[(2-hydroxy-ethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxy-benzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methyl-benzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylene-dioxybenzene, 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, 2,3-indolinedione, 1,3-diamino-4-(hydroxypropoxy)benzene, 1,3-diamino-4-(2-methoxyethoxy)benzene and 2,6-dihydroxy-3,4-dimethyl-pyridine.

Although the advantageous properties of the 3-(2,5-diaminophenyl)acrylamide derivatives of formula (I) described herein suggest that they should be used as the only developers, the 3-(2,5-diaminophenyl)acrylamide derivatives of formula (I) can, of course, also be used together with known developers, for example 1,4-diaminobenzene, 2,5-diaminotoluene, 1-(2,5-diaminophenyl)ethanol, 2-(2,5-diaminophenyl)ethanol, 4-aminophenol and derivatives thereof, for example 4-amino-3-methylphenol, 4,5-diaminopyrazole derivatives, for example 4,5-diamino-1-(2-hydroxyethyl)pyrazole, 4,5-diamino-1-benzylpyrazole and 4,5-diamino-1-(4-methylbenzylpyrazole, or tetraaminopyrimidines.

The couplers and developers can be present in the colorant of the invention either individually or in admixture with one another, the total amount of each of the couplers and developers in the colorant of the invention being about 0.005 to 20 wt. % preferably about 0.01 to 5 wt. % and particularly 0.1 to 2.5 wt. % (based on the total amount of colorant).

The total amount of the developer-coupler combination contained in the colorant described herein is preferably about 0.01 to 20 wt. %, an amount of about 0.02 to 10 wt. % and particularly 0.2 to 6 wt. % being particularly preferred. In general, the developers and couplers are used in approximately equimolar amounts, but it is not disadvantageous if the developer is present in a certain excess or deficiency.

Moreover, the colorant of the invention can additionally contain other dye components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, as well as common direct dyes, for example triphenylmethane dyes such as 4-[(4′-aminophenyl)-(4′-imino-2″,5″-cyclohexadien-1″-ylidene)methyl]-2-methylaminobenzene monohydrochloride (Color Index [C.I.] 42 510) and 4-[(4′-amino-3′-methylphenyl)-(4″-imino-3″-methyl-2″,5″-cyclohexadien-1″-ylidene)methyl]-2-methylaminobenzene monohydrochloride (C.I. 42 520), aromatic nitro dyes 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-nitrophenol and 1-(2′-ureidoethyl)amino-4-nitrobenzene, azo dyes such as sodium 6-[(4′-aminophenyl)azo]-5-hydroxynaphthalene-1-sulfonate (C.I. 14 805) and disperse dyes, for example 1,4-diaminoanthraquinone and 1,4,5,8-tetraaminoanthraquinone. The colorants of the invention can contain these dye components in an amount from about 0.1 to 4 weight percent.

The couplers and developers as well as the other dye components, provided they are bases, can, of course, also be used in the form of their physiologically tolerated salts with organic or inorganic acids, for example hydrochloric acid or sulfuric acid, or—if they contain aromatic OH groups—in the form of their salts with bases, for example as alkali metal phenoxides.

Moreover, if the colorants are to be used for coloring hair, they can also contain other common cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, as well as perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and hair-care agents.

The colorant of the invention can be in the form of, for example, a solution, particularly an aqueous or aqueous-alcoholic solution. A particularly preferred formulation form, however, is a cream, gel or emulsion. Such a composition consists of a mixture of the dye components and the usual additives employed for such compositions.

Common additives to solutions, creams, emulsions or gels are, for example solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerol or glycols such as 1,2-propylene glycol, moreover wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surface-active agents, for example fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides and ethoxylated fatty esters, furthermore thickeners such as the higher fatty alcohols, starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids, also hair-care agents such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The cited constituents are used in amounts commonly employed for such purposes, for example the wetting agents and emulsifiers at a concentration of about 0.5 to 30 wt. %, the thickeners in an amount from about 0.1 to 30 wt. % and the hair-care agents at a concentration from about 0.1 to 5.0 wt. %.

Depending on the composition, the colorant of the invention can be weakly acidic, neutral or alkaline. In particular, it has a pH of 6.5 to 11.5. Adjustment to a basic pH is preferably done with ammonia, but it can also be done with an organic amine, for example monoethanolamine and triethanolamine, or with an inorganic base such as sodium hydroxide and potassium hydroxide. Suitable for adjustment to an acidic pH are inorganic or organic acids, for example phosphoric acid, acetic acid, citric acid or tartaric acid.

For oxidative dyeing of hair, the afore-described colorant is mixed with an oxidant just before use, and the resulting mixture is applied to hair in an amount sufficient for the hair-dyeing treatment, in general about 60 to 200 grams, depending on the hair fullness.

Suitable oxidants for developing the hair coloration are mainly hydrogen peroxide or its products of addition to urea, melamine, sodium borate or sodium carbonate, in the form of a 3-12%, preferably 6% aqueous solution, atmospheric oxygen also being suitable. When a 6% hydrogen peroxide solution is used as oxidant, the weight ratio of hair colorant to oxidant is from 5:1 to 1:2, but preferably 1:1. Larger amounts of oxidant are used primarily at higher dye concentrations in the hair colorant or when strong bleaching of the hair is wanted at the same time. The mixture is allowed to act on the hair at 15 to 50° C. for about 10 to 45 min, preferably 30 min, after which the hair is rinsed with water and dried. Optionally, following this rinsing, the hair is washed with a shampoo and optionally post-rinsed with a weak organic acid, for example citric acid or tartaric acid. The hair is then dried.

The colorants of the invention containing a 3-(2,5-diaminophenyl)acrylamidederivative of formula (I) as developer give hair colorations of excellent color stability, particularly in terms of light fastness, wash fastness and rubbing fastness. As far as the dyeing properties are concerned, the hair colorants of the invention provide a wide range of different color shades from blond to brown, purple, violet and even blue and black, depending on the kind and composition of the dye components. These shades have unusual color intensity. The very good coloring properties of the hair colorants of the present patent application also manifest themselves in that these colorants make it possible to dye gray keratin fibers, particularly human hair, previously not damaged chemically, without any problems and with good covering power.

The following examples illustrate the object of the invention in greater detail without limiting its scope.

I. Preparation Examples