FI58432C - HAORFAERGNINGSMEDEL SOM BASERAR SIG PAO OXIDATIONSFAERGAEMNEN - Google Patents

Description

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Patent · och regittentyralaan v 'Anrtkan utltfd och utUkrlfwn publicarad 31.10.80 (32) (33) (31) Pyydetty atuolkwt —Begird prlorltat 29.11.73 02.10.7 ^ Federal Republic of Germany-Förbunds-republiken Tyskland (DE) P 2359399-9 P 2i + i + 7017 · 5 (71) Henkel Kommanditgesellschaft. auf Aktien, Henkelstrasse 67, UOOO Dussel-Dorf, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) David Rose, Dusseldorf-Holthausen, Ferdi Saygin, Erkrath, Erwin Weinrich, Dusseldorf-Holthausen, Federal Republic of Germany-Förbunds-Republika )

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(7 ^) Leitzinger Oy (5M Hair dye based on oxidative dyes - Härfärgnings-medel, som baserar sig pä oxidationsfärgämnen

The invention relates to a hair dye which is based on oxidative dyes and which optionally also contains conventional developers and other dyes.

In hair dyeing, the so-called oxidation dyes, which are generated by the oxidative-coupling of the developer component and the coupling component, play a primary role due to their efficient coloring and very good durability properties. Nitrogen bases such as p-phenylenediamine derivative, diaminopyridine, 1 * -aminopyrazine derivative, heterocyclic hydrazone are generally used as developing components. As the so-called potency components, m-phenylene diamine derivative, phenol, naphthol, resorcinol derivative and pyrazolone are mentioned.

The oxidative dye components of good hair should primarily meet the following conditions:

They must form the desired color tone strong enough to oxidatively join the developer and coupling component together. Their absorption properties to the hair must still be adequate - very good and, in addition, they must be harmless in a toxic and skin irritating sense.

Substituted or unsubstituted p-phenylenediamines conventionally used as a developer have the disadvantage of causing skin irritation and consequent severe allergies in some individuals. In order to avoid these skin irritating disadvantages, the recently proposed developers are not always completely satisfactory in terms of their technical properties.

The colorants according to the invention avoid the above-mentioned drawback, which colorant is characterized in that it contains tetraaminopyrimidines of the general formula * 5, E6 \ /

OF

r 1 AA <R 3 wherein R 1 - represents hydrogen, an alkyl group having 1 to U carbon atoms, a group - (CH 2) n ~ X »where n = 1-U and X is a hydroxyl group, a halogen atom, a group -NH 2, NHR 'and -NR 'R ", wherein R' and R" may represent an alkyl group of 1 to U carbon atoms or together with a nitrogen atom a heterocyclic ring which may contain an additional nitrogen atom or an oxygen atom, an optionally substituted aryl group, an optionally substituted heterocyclic 5- or 6-membered ring, having one or two nitrogen atoms or a nitrogen atom and an oxygen atom, and their inorganic or organic salts as developing agents and coupling agents.

The use of the compounds according to the invention as developing components, together with the coupling components commonly used in oxidative hair dyeing, provides a wide variety of strong color tones which have not been possible with these components and the hitherto known developing agents and thus substantially improve the oxidative coloring possibilities of the hair. In addition to the very good durability properties of the dyes obtained by these dyes, the tetraaminopyrimidines according to the invention are characterized by good water solubility, good storage life and safety in a toxic as well as skin irritant sense.

The tetraaminopyrimidines used as developing components according to the invention can be used either as such or in the form of their salts with inorganic or organic acids, such as, for example, chloride, sulphate, phosphate, acetate, propionate, tin, citrate.

The preparation of most of the tetraaminopyrimidines used as development components according to the invention is already known from the literature and can be found in D.J. Brovmin's monograph, "The Pyrimidines" in the series Heterocyclic Compounds, Interscience Publishers (1962), Volumes I and II. Only a few of the compounds used represent new supplements, the preparation of which has been separately described.

For the synthesis of the compounds according to the invention, the starting point is generally 2,4,6-triaminopyrimidines, to which the 5-amino group is added by nitrogenation and subsequent reduction, which can also be started from correspondingly substituted triamino-alkylalkaptopyrimidines and substituted by an alkyl mercapto group. The latter method is particularly suitable for placing amino groups or substituted amino groups in the 2-, 4- or 6-position of the pyrimidine ring.

The development components used according to the invention are, for example, 2,4,5, bt etraamino, 4,5-diamino-2,6-bismethylamino, 2,5-diamino-4, o-bismethylamino, 4 , 5-diamino-6-butylamino-2-dimethylamino, 2 ', 5-diamino-4-diethylamino-6-methylamino, 4,5-diamino-6-diethylamino-2-d dimethylamino, 4,5-diamino-2-dimethylamino-6-methylamino, 4,5-diamino-2-dimethylamino-6-ethylamino, 4,5-diamino-2-dimethylamino -6-Isopropylamino, 4,5-diamino-2-imylamino-6-methylamino, 4,5-diamino-C-dimethylamino-2-methylamino, 4,5-diamino-2-dimethylamino - 6-propylamino, 2,4,5-triamino-6-dimethylamino, 4,5,6-amino-2-dimethylamino, 2,4,5-triamino-6-methylamino -, 4,5 * f-triamia income style amino-, 4,5-diamino-2-dimethylamino-6-piperidino, 4,5-diamino-6-methylamino-2- Piperidino-, 2,4,5-triamino-6-Piperidino-, 2,4,5-triamino-6-anilino-, 2,4,5-triamino-6-Bent Cause 1 amino, 2,4,5-triamino-6-benzylideneamino, 4,5,6-Triamino-2-piperidino-, 2,4,6-trismethylamino-5-amino-, 2,4,5-triamino-6-di-n-propylamino-, 2,4,5 -triamino-C-morpholinyl, 2,5,6-triamino-4-dimethylamino, 4,5,6-triamino-2-morpholino-58432-, 2,4,5-triamino-6 -8-hydroxyethylamino, 4,5,6-triamino-2-8-aminoethylamino, 2,5,6-triamino-4-8-methylaminoethylamino, 2,5-diamino-4, ε-bis-γ-diethylamino-propylamino, 4,5-diamino-2-methylamino-6-8-hydroxyethylamino, 5-amino-2,4,6-triethylamino, 2,4-bis-3-hydroxyethylamino 6-anilino-5-amino-pyrimidine.

Examples of coupling components used as hair dyes according to the invention are: α-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, pyrocatechol, pyro -gallol, 1,5- or 1,7-dihydroxy-naphthalene, 5-amino-2-methylphenol, hydroquino, 2,4-diaminoanisole, m-toluenediamine, 4-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-Phenyl-3-methyl-pyrazolone-5,1-phenyl-3-amino-pyrazolone-5,1-phenyl-3,5-diketo-pyrazolidine, 1-methyl-7-dimethylamino-4-hydroxy- quinolone-2,1-amino-3-acetacetylamino-4-nitrobenzene or 1-amino-3-cyanoacetylamino-4-nitrobenzene.

In order to obtain tones that are as intense as possible and as close as possible to natural hair tones, a full-blown blue dye is very important as a tinting component. However, when natural tones are achieved with the aid of blue color components, difficulties arise with the use of conventional blue coupling components, even with the use of generally very satisfactory tetraaminopyrimidines as developing agents.

It has now been found that this shortcoming can be remedied if m-aminophenols having the general formula are used as the coupling component with tetraaminopyrimidine as a developer.

OH

x

»R, K

Y

wherein X and / or Y represent hydrogen, a halogen atom, a hydroxyl group, an amino group, an alkyl, alkoxy, alkylamino or dialkylamino group having 1 to 4 carbon atoms, 5 58432 R 1, hydrogen, an alkyl group having 1 to 10 carbon atoms, optionally substituted a phenyl group, a benzyl group, a methylene cyanamide group, a propionamido group, a ureido group, a thioureido group, an oxalyl ester group having 1 to 4 carbon atoms, a group (Cl and NR'R ", wherein R 'and R" are alkyl groups having 1 to 4 carbon atoms, further R 1 and R 6 may be taken together with the nitrogen atom to form an optionally substituted heterocyclic 5- or 6-membered ring which may contain one additional nitrogen atom or an oxygen atom, and R 2 is the same as R 1, but not hydrogen.

The m-aminophenol derivatives used as the blue coupling component can be used either as such or in the form of their salts with inorganic or organic acids, such as, for example, chloride, sulfate, phosphate, acetate, propionate, lactate, citrate.

Examples of the blue coupling component dyes according to the invention are 3-dimethylaminophenol, 3-diethylaminophenol, 3-dioctylaminophenol, 3-methylethylaminophenol, 3-ethylpropylaminophenol, 3-phenylethylaminophenol, 3-phenylethylaminophenol, 3-phenylethylaminophenol, 3-phenylethylaminophenol, -methylaminophenyl, 3-ethylaminophenol, 3-octylaminophenol, 3-ethylureidoaminophenol, 3-ureidophenol, 3-phenylureidoaminophenol, 3- (β-hydroxyethylamino) -phenol, 3- (N-methyl-Ng-hydroxyethylamino) -phenol) -phenol , N-ethyl-N- (3-hydroxyphenyl) urea, 3-methylenecyanamidophenol, 3 - ((2- (diethylamino) ethyl) amino) phenol, 3-N- (2-diethylaminoethyl) -N -methylaminophenol, 3-pyrrolidinophenol, 3-morpholinophenol, 3-piperidinophenol, 2-methyl-5-ethylaminophenol, 2-methyl-5-diethylaminophenol, 4-methoxy-3-ethylaminophenol, 4-methoxy-3 -diethylaminophenol, 2-chloro-5-dimethylamino-phenol, 3,5-dihydroxy -N, N-dimethylaniline, 2-amino-5-diethylamino-phenol, 3-diethylamino-5-hydroxy-6-chlorotoluene, 3-anilino-5-hydroxy-6-chloro-toluene, 3-piperidino-5-methyl -phenol, 3-pyrrole-dino-4-chlorophenol.

The preparation of m-aminophenol derivatives for use as blue coupling component dyes according to the invention is known in the literature from F. Effen-Berger, G. Prossel, E. Auer and P. Fischer, Chemical Publication 103 (1970), pp. 1456-62 as well as from British Patent Publication No. 58432 to 974. 343. A few derivatives not yet used in the manufacture of components are described separately.

The hair colorants according to the invention generally use developer components in approximately molar amounts relative to the coupling components used. Although the use of moles proves to be appropriate, it is not a disadvantage if the developer component is used in a given overdose or underdose.

Furthermore, it is not necessary that the developer component and the coupling component form a single product, and further, the developer components may be mixtures of the tetraaminopyrimidines used according to the invention, as may the coupling components be mixtures of the above-mentioned coupling components.

In addition, the hair dyes of the invention may contain other known and conventional developer components as well as conventional dyes, if this is necessary to provide certain color variations.

Oxidative coupling, i.e. the development of coloring, can in principle take place as with other oxidative hair dyes with the aid of atmospheric oxygen. However, chemical oxidizing agents are expediently used. These are, in particular, hydrogen peroxide or its urea, melamine and sodium borate compounds, as well as mixtures with such hydrogen peroxide connection compounds and potassium peroxide disulphate.

As developer components, the tetraamino-pyrimidines according to the invention then have the advantage that they give satisfactory color results even in the case of oxidative coupling without oxygen, and thus damage to the hair can be avoided by the oxidizing agents otherwise commonly used in oxidative coupling. However, if a hair whitening effect is desired at the same time as coloring, the presence of oxidizing agents is necessary.

The hair dyes according to the invention are prepared for use as corresponding cosmetic products, such as creams, emulsions, gels or also as simple solutions, and are added to them immediately before application to the hair by one of said oxidizing agents. The concentration of this type of dye preparation with respect to the oxidation arms is 0.2 to 5% by weight, preferably 1 to 3% by weight. To prepare creams, emulsions or jellies, the dye components are mixed with other ingredients customary for preparations of this type. Such additives include, for example, wetting or emulsifying agents of the anionic or non-ionizable type, such as alkyl benzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, ethylene oxide deposition products in fatty alcohols, precipitating agents such as -alcohols, paraffin oil, fatty acids, further perfume oils and hair conditioners such as pantothenic acids and cholesterol. These additives are then used for this purpose in conventional amounts, such as, for example, a wetting and emulsifying agent in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight, in each case based on the weight of the total mixture.

The use of the hair dyes according to the invention, whether in the form of a solution, emulsion, cream or jelly, can take place in a weakly acidic, neutral or, in particular, alkaline environment at pH 8-10. The operating temperatures then range from 15 to 40 ° C. After a duration of action of about 30 minutes, the hair dye is removed from the hair to be dyed. The hair is then washed with a mild shampoo and dried.

The color shades provided by the hair dyes of the invention show exceptional variations in the use of various developer and coupling components, ranging from light yellow to dark brown and green to purple. The dyes obtained have good light, washing and abrasion resistance properties and are again easily removed with the aid of reducing agents.

The following examples further illustrate the subject matter of the invention.

examples

The following describes the preparation of some of the tetraaminopyrimidines used in the hair dyes of the invention, which are not known in the literature to date.

Preparation of 2,4,6-trimethylamino-5-aminopyrimidine sulfate, C 1-6 H 2 N 2 O 2 SO 2 .2 HO, 8 58432 X) 5.5 g of 2,4,6-trimethylaminopyrimidine was dissolved in 50 ml. water and adjusted to nH 4 with sodium acetate. The solution was heated to 80 ° C and a solution of 1.4 g NaNO 3 in 5 mL was added. A red solution formed. At 60 ° C, enough sodium dithionite was added that the solution turned yellow. Diluted i 2 SO 4 was added to the yellow solution and the precipitate was sucked off. Yield 55%.

Flash point 215 °

Analysis:% C% H% N

calculated: 26.6 6.4 26.6 obtained: 26.6 8.3 27.7 x) J. Winkelmann's "Prakt. Chem." 115, 292, (1927).

Preparation of 2.4.5-triamino-6-di-n-propylaminopyrimidine dihydrochloride, C10H20N6 '2 Hc1 2.4.5-Triamino-6-di-n-propylamino-pyrimidine chloride was prepared stepwise as follows: 1. 2,4-diamino-6-di -n-propylamino-pyrimidine X) 15 g of 2,4-diamino-6-chloropyrimidine were added to 130 ml of ethanol with 50 g of di-n-propylamine and kept in an autoclave for 3 hours at 200 ° C (initial pressure 10 atj). After cooling and opening, the reaction mixture was cooled in an ice-brine bath to separate di-propylamine hydrochloride. This was followed by filtration and thorough evaporation of the mother liquor (residue ca. 30 ml) to give 18 g = 82.9% of crude product; this was further worked on as such.

2. 2,4-Diamino-5-nitroso-6-di-n-propylaminopyrimidine 18 g of 2,4-diamino-6-di-n-propylaminopyrimidine (crude preparation) were slurried in 25 ml of water and as much glacial acetic acid was added. that a pH of 4 was reached; then warmed to 50 °, at which time the additive had dissolved and 5.5 g of sodium nitrite in 10 ml of water were slowly added; after a short time, a raspberry-red precipitate separated; sucked off and dried in vacuo at room temperature to give a residue of 9.4 g = 46%.

Melting point: 206-208 ° C

Analysis:% C% H% N

calculated 50.40 7.61 35.27 obtained 49.56 7.62 35.50 3. 2,4,5-triamino-6-di-n-propylamino-pyrimidine dihydrochloride 6.5 g 2,4-diamino-5 -nitroso-6-di-n-propylaminopyrimidine was hydrogenated in 150 ml of ethanol with 0.5 g of catalyst (10% Pd on carbon) at room temperature in a shaking flask. After completion of the hydrogenation, it was filtered over a catalyst, acidified with hydrochloric acid and evaporated.

Residue: 5.6 g = 78.8%, brown crystals, decomposition point: 105 ° C. the phase spectrum shows a molecular weight of 224 (calculated 224).

x) Prepared by B. Rothin, J.M. Smith and E.M. According to Hultquist, "J. Am. Chem. Soc.", 12, 1914 (1950).

2.4.5- Preparation of triamino-6-morpholino-pyrimidine sulphate, C8H14N6 ° 'H2SO4' 2.4.5-Triamino-6-morpholino-pyrimidine sulphate was prepared in stages from the following compounds: x) 1. To 10 g of 2,4-diamino- 6-Chloropyrimidine (0.07 mol) was added to 30 g of morpholine (30 ml (0.34 mol)) and heated to 100 ° C with stirring for 1 hour; the mixture was kept at this temperature for 2 1/2 hours; then 10 ml of ethanol was added and allowed to refrigerate until the morpholine hydrochloride had separated, which was separated. The filtrate was evaporated to give a crude semi-oily, semi-crystalline residue (5.9 g = 43.7%); the crude preparation was further processed.

2. 2,4-Diamino-6-morpholino-5-nitroso-pyrimidine 5.9 g of 2,4-diamino-6-morpholino-pyrimidine (0.03 mol) (crude preparation) were dissolved in 25 ml of water by heating and adding acetic acid until pH 4 was reached; the solution was then heated to 80 ° C by the slow addition of 2 g of sodium

a solution of nitrite in 5 ral of water; after a short time, the nitroso compound separated as a raspberry red precipitate; evaporation and cooling gave a total of 4.1 g = yield of $ 60.3, pour point: 231-233 ° G

Analysis:% G% U% K

calculated: 42.85 5.39 37.48 obtained: 41.92 4.97 38.2? 3 # 2,4,5-Triamino-6-morpholino-pyrimidine sulfate 2.5 g of 2,4-diamino-6-morpholino-5-nitroso-pyrimidine was slurried in 15 ml of water and 2N HGL (5 ml) was added until the supplement was completely 1created; the additional mixture was then heated to 50 ° and sodium dithionite (Na 2 O 2) was slowly added so that the purple solution became color; it was then filtered, cooled and adjusted to pH 2 with sulfuric acid (1: 1).

After a short time, pyrimidine precipitated as sulfate; 2.6 g = 76.4% were obtained.

Analysis: (recrystallized):% G% K% N

calculated: 31.17 5.23 27.25 obtained: 29.81 4.98 27.86

Melting point: sintered at 230 °, slow decomposition from 255 ° G, x) Prepared by B, Rothin, J.M. Smith and E.M. Hultquistin "J. Am.

Ghem. Soc. ", 72, 1914 (1950), other tetraaminopyrimidines used in the following examples are known in the literature and are prepared as described in DJ Brown's monograph" The Tyrimidines "as heterocyclic compounds," Intercsience Publishers ", 1962 Volumes I and II.

The following describes the preparation of a few hitherto unknown m-aminophenol derivatives which are used in the hair dyes according to the invention as blue component dyes.

1. 4-Methoxy-3-diethylaminophenol

To a solution of 10.5 g of 4-methoxy-3-aminophenol in 50 ml of ethanol was added 8.3 g of ethyl bromide. The reaction mixture was then heated to reflux for 24 hours. After cooling, it was diluted with 800 ml of water, and by adding sodium carbonate, the solution was made slightly alkaline. The solution was re-extracted with ether, and the combined extracts were dried over anhydrous sodium sulfate. After filtration, the residue was evaporated and the remaining residue was taken up in 50 lanes of ethanol and, after the addition of 8.7 g of ethyl bromide, was alkylated again as described above and worked up.

This time, after drying, the ether extract was evaporated to a volume of only about 500 ml, and dry JCl gas was now introduced into this solution under cooling. the precipitate was filtered off with suction, the residue was dried and dissolved in ethanol and treated with activated carbon. Addition of ether to the ethanolic solution gave the pure product.

Melting point: 197-198 ° G

Analysis: G H N 01 calculated: 57.1 7.8 6.05 15.5 obtained: 56.5 - 7.8 5.4 14.6

Mass spectrum: 195 (calculated 195).

2. 2-methyl-5-diethylaminophenol

A solution of 50 g of 5-amino-2-methylene in 250 ml of ethanol was heated under reflux for 4 hours after the addition of 88.6 g of ethyl bromide. After cooling, the solution was diluted with 1 L of water, made slightly alkaline with sodium carbonate and then extracted repeatedly with ether. The letter extract was dried and evaporated. The residue was recrystallized from ethanol, Melting point: 128-129 ° C

Analysis: C H 'N

calculated: 71.5 8.6 9.3 obtained: 70.79 8.51 9.5 class spectrum: 151 (calculated 151) 5. 2-methyl-5-diethylaminophenol 5 g of 2-methyl-5-ethylaminophenol were dissolved in 50 ml in ethanol and, as described in 1), was alkylated with 5.2 g of ethyl bromide and then worked up.

Melting point: 192 ° C

Analysis: C II N 01 calculated: 61.5 8.4 6.5 16.5

found: 62.9 8.8 6.8 15, Q

ivlass spectrum: 179 (calculated 17 ^) 58432 1. Preparation of 2,4,5, -triamino-6-g-hydroxyethylaminopyrimidine

Step A. Preparation of 2,4-diamino-6-g-hydroxyethylaminopyrimidine dihydrochloride.

2.5 g of 2,4-diamino-6-chloropyrimidine, prepared according to the information obtained from Gabriel in "Berichte der Deutschen Chemischen Gesellschaft" No. 34 (1901), page 3362, was heated together with 2.5 g monoethanolamine for 30 minutes to 140 ° C. The mixture was then dissolved in 100 ml of ethanol and hydrogen chloride was introduced. The precipitate was sucked off and washed with ethanol to give 3.2 g of a light brown powder with a melting point of 205 ° C and a molecular weight of 241 in a mass spectrograph. It formed 2,4-diamino-6-g-hydroxyethylaminopyrimidine dihydrochloride.

Step B. 2,4-Diamino-6-g-Hydroxyethylamino-6-p-chlorophenylazopyrimidine.

3.2 g of 2,4-diamino-6-g-hydroxyethylaminopyrimidine was dissolved in 65 ml of water, and to this solution was added a saline hydrochloric acid solution of diazotized chloroaniline (starting amount 1.67 g of chloroaniline) at 0 ° C. 3.8 g of yellow 2,4-diamino-6-g-hydroxyethylamino-5-p-chlorophenylazopyrimidine with a melting point of 235 ° C were obtained.

Step C. 2,4,5-Triamino-6-g-hydroxyethylaminopyrimidine sulfate 3.4 g of 2,4-diamino-6-g-hydroxyethylamino-5-p-chlorophenylazopyrimidine was catalytically hydrogenated in 70 ml of ethanol under 50 atm overpressure. At 90 ° C in the presence of a Raney nickel catalyst. After completion of the dehydration, 4 ml of glacial acetic acid were added and the catalyst was filtered off. The solution was evaporated to dryness, the residue was dissolved in ether, filtered and dissolved in 20 ml of water. After adding 2 ml of concentrated sulfuric acid, the precipitate was filtered off with suction and washed with calcium chloride. 0.5 g of 2,4,5-triamino-6-g-hydroxyethylaminopyrimidine sulphate with a melting point of 198-199 ° C was obtained.

13,58432 2. 4,5-Diamino-2,6-bis-methylaminopyrimidine

The preparation was carried out according to the information given by Beon in "Journal of the Chemical Society" (1957) page 2146. The melting point of the product was 182 ° C.

3. 2,6-Bis-hydroxyethylamino-4-methylamino-5-aminopyridine

Step A. 2,6-Bis-hydroxyethylamino-4-chloropyrimidine 250 ml of a 33% ethanolamine solution in ethanol was added dropwise to 50 g of 2,4,6-trichloropyrimidine in ethanol under cooling. The mixture was then heated at reflux for 5 hours, cooled and sucked off. Recrystallization from water gave 51.2 g (80.7% of theory) of 2,6-bis-hydroxyethylamino-4-chloropyrimidine, m.p. 150-153 ° C.

Step B. 2,6-Bis-hydroxyethylamino-4-chloro-5- (p-chlorophenylazo) -pyrimidine 28.1 g of chloroaniline were diazotized and added to 51 g of 2,6-bis-hydroxyethylamino-4-chloropyrimidine. After sodium acetate was added and the mixture was allowed to stand for one day, the compound precipitated and was recrystallized from ethanol. 54 g of 2,6-bis-hydroxyethylamino-4-chloro-5- (p-chlorophenylazo) -pyrimidine (67% of theory) with a melting point of 199-202 ° C were obtained.

Step C. 2,6-Bis-8-hydroxyethylamino-4-methylamino-5- (p-chloro-phenylazo) -pyrimidine 1 g of 2,6-bis-hydroxyethylamino-4-chloro-5- (p-chloro-phenylazo) - pyrimidine, 120 ml of a 33% ethanolic methylamine solution and 150 ml of ethanol were heated in an autoclave for 24 hours at 150-160 ° C. The contents of the autoclave were then mixed with twice the amount of water, filtered off with suction and recrystallized from water. 20.7 g (87.7% of theory) of 2,6-bis-hydroxyethylamino-4-methylamino-5- (p-chlorophenylazo) pyrimidine with a melting point of 159-161 ° C were obtained.

14,584 32

Step D. 2,6-Bis-8-hydroxyethylamino-4-methylamino-5-aminopyrimidine 20 g of 2,6-bis-hydroxyethylamino-4-methylamino-5- (p-chlorophenylazo) pyrimidine were hydrogenated in 300 ml. ethanol in the presence of 3 g of Raney nickel at 90-95 ° C under an excess pressure of 50 atm of hydrogen gas for 5 hours. To the contents of the autoclave was added 16 ml of concentrated acetic acid, evaporated in vacuo, the residue was dissolved several times in ether, filtered off with suction and dried. Recrystallization from ethanol gave 5 g (38.5% of theory) of 2,6-bis-hydroxyethylamino-4-methylamino-5-aminopyrimidine, m.p. 145-150 ° C.

4. 2,6-Bis- g-hydroxyethylamino-4-dimethylamino-5-aminopyrribidine

Step A. 2,6-Bis-8-hydroxyethylamino-4-chloropyrimidine To 100 g of 2,4,6-trichloropyrimidine was added dropwise 500 ml of a 33% alcoholic ethanolamine solution under cooling. After refluxing for 4 hours, the mixture was cooled, filtered off with suction and recrystallized from water. 97.2 g (76.6% of theory) of 2,6-bis-6-hydroxyethylamino-4-chloropyrimidine with a melting point of 149-152 ° C were obtained.

Step B. 2,6-Bis-β-hydroxyethylamino-4-chloro-5- (p-chloro-phenyl-azo) -pyrimidine 99 g of 2,6-bis-g-hydroxyethylamino-4-chloropyrimidine were added to 54.6 g: diazotized p-chloroaniline. Recrystallization from ethanol gave 154 g (97.5% of theory) of 2,6-bis--hydroxyethylaminochloro-5- (p-chlorophenylazo) -pyrimidine, m.p. 194-196 ° C.

Step C. 2,6-Bis-g-Hydroxyethylamino-4-dimethylamino-5- (p-chloro-phenylazo) -pyrimidine 1 g of 2,6-bis-g-hydroxyethylamino-4-chloro-5- (p-chlorophenyl) azo p-Pyrimidine and 72.9 g of a 33% ethanolic dimethylamine solution were stirred for 8 hours at room temperature. After standing overnight, the mixture was sucked and recrystallized from ethanol. 14.3 g (69.8% of theory) of 2,6-bis-15,58432 hydroxyethylamino-4-dimethylamino-5-chlorophenylazo] -pyrimidine with a melting point of 157-158 ° C were obtained.

Step D. 2,6-Bis-β-hydroxyethylamino-4-dimethylamino-5-aminopyrimidine 28 g of 2,6-bis-β-hydroxyethylamino-4-dimethylamino-5- (p-chlorophenyl-azo) -pyrimidine were hydrogenated. In 400 ml of ethanol in the presence of 4 g of Raney nickel at 90-95 ° C with a hydrogen gas pressure of 50 atm overpressure. After filtering off the Raney nickel, the residual oil was dissolved in ether washed with hydrochloric acid, the hydrogen chloride was evaporated and made to crystallize. It was then stirred with methanol and sucked under a nitrogen gas atmosphere. 8 g (26.9% of theory) of 2,6-bis-β-hydroxyethylamino-4-dimethylamino-5-aminopyrimidine were obtained. Melting point from 172 ° C, decomposition.

5. 2,4,6-Tris-p-hydroxyethylamino-5-aminopyrimidine

Steps A and B are similar to Steps A and B of Example 4.

Step C. 2,4,6-Tris-3-hydroxyethylamino-5- (p-chlorophenylazo) -pyrimidine

A mixture of 20 g of 2,6-bis-g-hydroxyethylamino-4-chloro-5- (p-chlorophenylazo) -pyrimidine and 100 g of a 33% ethanolamine solution containing ethanol was boiled for 4 hours. After cooling, twice the amount of water was added, the mixture was allowed to stand for 3 hours, sucked off and the precipitate was washed with water. 19 g (93.8% of theory) of 2,4,6-tris-β-hydroxyethylamino-5- (p-chlorophenylazo) -pyrimidine with a melting point of 152-155 ° C were obtained.

Step D. 2,4,6-Tris-8-hydroxyethylamino-5-aminopyrimidine 19 g of 2,4,6-tris-8-hydroxyethylamino-5- (p-chlorophenylazo) -pyrimidine were hydrogenated in 100 ml of ethanol 2 g: n in the presence of Raney nickel as a catalyst at a temperature of 90 to 95 ° C under an overpressure of 50 atm of hydrogen gas. When the dehydrogenation was completed, 20 ml of concentrated acetic acid, filtered off from Raney nickel, were added, 16,58432 were evaporated, washed with ether and, after adding dilute hydrochloric acid and evaporated once more, the crystals were filtered off and dried using phosphorus pentoxide. 5.2 g (31.3% of theory) of 2,4,6-tris-β-hydroxyethylamino-5-aminopyrimidine with a melting point of 149-154 ° C were obtained.

6. 2,6-Bis-dimethylamino-4-g-hydroxyethylamino-5-aminopyrimidine

Step A. 2,6-Bis-dimethylamino-4-chloropyrimidine 100 g of 2,4,6-trichloropyrimidine was added under cooling to 500 ml of a 33% ethanolic dimethylamine solution and allowed to stand overnight at room temperature. After suction, wash with water. 98.6 g (90.2% of theory) of 2,6-bis-dimethylamino-4-chloropyrimidine with a melting point of 53-54 ° C were obtained.

Step B. 2,6-Bis-dimethylamino-4-chloro-5- (p-chlorophenylazo) -pyrimidine 65.3 g of p-chloroaniline were diazotized and acidified to 102 g of 2,6-bis-dimethylamino-4-chloropyrimidine. . 103.3 g (59.9% of theory) of 2,6-bis-dimethylamino-4-chloro-5- (p-chlorophenylazo) -pyrimidine with a melting point of 87-89 ° C were obtained.

Step C. 2,6-Bis-dimethylamino-4-O-hydroxyethylamino-5- (p-chloro-phenylazo) -pyrimidine

A mixture of 25 g of 2,6-bis-dimethylamino-4-chloro-5- (p-chloro-phenylazo) -pyrimidine, 45.1 g of ethanolamine and 90 ml of ethanol was boiled for 4 hours. After cooling, the mixture was filtered and the precipitate was dried. 26.5 g (93.3% of theory) of 2,6-bis-dimethylamino-4-hydroxyethylamino-5- (p-chlorophenylazo) -pyrimidine with a melting point of 115-118 ° C were obtained.

17 5 8 4 3 2

Step: D. 2,6-Bis-dimethylamino-4-g-hydroxyethylamino-5-aminopyrimidine hydrochloride dihydrate 26 g of bis-dimethylamino-4-hydroxyethylamino-5- (p-chlorophenylazo) -pyrimidine were hydrogenated in 375 ml of ethanol in 3 g of ethanol. in the presence of nickel as a catalyst at a temperature of 90 to 95 ° C under a hydrogen gas pressure of 50 atm overpressure. When the dehydration was complete, 20 ml of concentrated acetic acid, filtered off from Raney nickel, were added, the residue was dissolved in dilute hydrochloric acid, re-evaporated and the residue was dissolved in ethanol. Recrystallization from a mixture of ethanol and dilute hydrochloric acid gave 6 g (30.3% of theory) of 2,6-bis-dimethylamino-4-hydroxyethylamino-5-aminopyrimidine hydrochloride dihydrate, m.p. 233 ° C.

The hair dyes according to the invention were used in the form of cream emulsions. In this case, one emulsion consisting of 10 parts by weight of fatty alcohols with chain lengths of C12-C18 and 10 parts by weight of fatty alcohol sulphate (sodium salt) with chain lengths of C12-C18 of 75 parts by weight of water in each case 0.01 mol of the tetra shown in the following table was mixed. -amino-pyrimidines and the coupling component. The pH of the emulsion was then adjusted to 9.5 with ammonia, and water was added to the mixture to bring it to 100 parts by weight. The oxidative coupling was performed either with atmospheric oxygen or using 1% hydrogen peroxide solution as the oxidizing agent, with 10 parts by weight of hydrogen peroxide solution being added to 100 parts by weight of the emulsion. The respective color cream, with or without oxidizing agents, was applied to a 90% grayed, not particularly pretreated, human hair, where it was allowed to stand for 30 minutes. At the end of the dyeing process, the hair was washed with a conventional hair detergent and then dried. The staining obtained in this context can be seen in Table 1 below.

18 58432

Table 1 [7 ~: -1--1--1

The resulting color is a significant color tone obtained by air oxidation with 1% I ^ Cgtta 1 2,4,5,6-tert-phenylenediamine olive olive ramaminopyrimidine 2 "2, 4 -diaminoanisole dark green dark green 3 "m-toluenediamine-yellow-brown-yellow-yellow-ni 4" m-aminophenol violet-brown violet-brown 3 resorcinol age 3-methyl-brown-brown-orange-li-pyrazolone 8 "resorcinol monomer-golden-brown golden-brown ether 9" -dimethyl-m-phenylenediamine yellow-brown yellow-brown amino-?, 5,6-triaminopyrimidine 13 "2; 4-diaminoanisole olive yellow olive yellow 14" m-toluenediamine-yellow-yellow-yellow-brown 1 I-m-aminophenol Burgund inp inpunainen ne n 7 0 "resorcinol brownish reddish n 17" 1-phenyl-3-amino raspberry red raspberry pyrazolone 18 "m-xenylenediamine olive brown olive brown 19 2-dimethyl-m-phenylenediamine 4,5-green-green-dark midine ε, (j "2: 4-diaminoanisole dark green dark green 21 | "m-toluenediamine-olive-pungent-olive-pungent-yellow-yellow; (22 j" m-aminophenol j-gray-purple gray-purple I "resorcinol | red-purple red-violet 24 i" 1-phenyl-3-amino-i brick red | brick red) | 5) jj 19 58432 ό3 i— Γ, .βίΐ ite I Coupling compo- Obtained color tone j mark ......... 'ki by air oxidation 1 λ: 11a 0 ^ 25 2-diraethyl-1-phenyl -3-methyl-lacquer red-gray amino-4,5,6-l-pyrazolone (5) triaminopyrimidine 26 "N-naphthol horse brown olive brown 27" 3-acetylacetam-yellowish brown brass yellow-1-amino- 4-Nitrobenzene 26 "1-Phenyl-3,5-dike-brown-orange gray-red n-to-pyrazolone 29" o-cresol brown-orange ivory 30 "m-cresol brown-orange ivory 31" 2,5-dimethylphenol: brown-gray-green li 32 "3f4-dimethylphenor brown orange gray-green li 33" 3 "5-dimethylphenor brown orange gray orange li 34" 1,5-dihydroxy brown r faithful naphthalene 35 11 pyrogallol chocolate brown metallic gray 36 "pyrocatechol reddish brownish grayish 37" 1-methyl-4-hydro-gray-orange golden light si-7-dimethylamino-quinolone -2 38 "5-amino-2-methyl-brown brown phenol 39 "hydroquinone brownish golden light 40; -piperidino-m" phenylenediamine dark green dark green i 4, 5,6-triaminopyrimidine 41 "rir-a minor eno li dark purple dark purple 42" resorcinol gray rubin 2: gray rubin 43 4-diaminoanisole dark green dark green 44 m-toluenediamine brown orange brown orange ni 45 "1-phenyl-3-aminocornate red tomato in red. pyrazolone (5) and 46 1-morpholino-m-phenylenediamine olive olive! 4,5, t-Triamino-amino-imine 4 7 '' m-aminophenol dark purple! Dark violet! 48 "resorcinol | ha r ma a. Nr ub i in i gray ruby 58432 se iisi- Developer Coupling- Obtained color tone flier k- tent ----------------- kif by air oxidation 1 f: : 11a HgOgCta 49 2-morpholino-2: 4-diaminoanisole dark green dark green 4,5,6-triaminopyrimidine 50 "m-toluyleneamine olive brown olive brown 51" 1-phenyl-3-amino-brown-red-brown 2-pyrazolone -methylamino-m-phenylenediamine olive olive no-4,5,6-triaminopyrimidine 53 "m-aminophenol dark purple dark purple 54" resorcinol gray-red-brown-purple 55 "2: 4-diaminoanisole dark green dark green 56" m-toluene 'yellow yellow ni 57 "1-phenyl-3-amino-brown-brown-brown pyrazolone (5) 58 O-morpholino-m-phenylenediamine olive brown olive brown 2.4.5-triaminopyrimidine 59" 2,4-diaminoanisole gray-green olive 60 "m- toluenediamine-gold-yellow brass-yellow 61 "m-aminophenol gray ruby gray red 62 "resorcinol brown red brown 63" 1-phenyl-3-amino-matt red matt red pyrazolone-5 64 6-piperidino-m-phenylenediamine bamboo yellow gray yellow 2,4,5-triaminopyrimidine 65 "2,4-diaminoanisole 66 "m-aminophenol olive brown bamboo yellow 67" resorcinol gray-red ivory 68 "ra-toluenediamine-gray-yellow olive brown ni <69" 1-phenyl-3-amino-gem yellow yellow yellow pyrazolone-5 70 6-d-phen-prime opine honey-yellow olive liamino-2,4,5-triaminopyrimidine 71 "2,4-diaminoanisole olive green olive 72" m-toluenediamine-honey-honey-honey olive ....... * - 1 21 58432 .usi- Development Coupling Composite Hue Constructive - by Oxidation Oxidation with 1 # IUO ^ ia 73 6-di-n * propy-4 m-aminophenol Gray Ruby Gray Ruby Liamino-2,4,5-triaminopyrimidine 74 "resorcinol brownish red" 1-phenyl-3-amino reddish brown red brown pyrazolone-5,746 2,4,6-trisme-m-phenylenediamine oak brown olive stylylamino-5-aminopyrimidine 77 "2,4-diarainoanisole olive light brown 78" m-toluenediamine-brass yellow-! olive 79 "m-aminophenol dark ruby brown 80" resorcinol gray red mild red 81 "1-phenyl-3-amino red brown light brown pyrazolone-5 82 2-dimethyl-3-diethylamino-black-blue black-blue Nino-4,5,6-. 'phenol triaminopyrimidine 83 "3-O-hydroxyethyl blue black black aminophenol 84" 3 ((2- (diethylamino black blue blue no) -ethyl) phenol 85 "3-morpholinophenol dark purple dark purple 86 3-ethyl; 4 black-blue black-blue minophenol 87 "3-butylamino-e-black-blue black-blue arrow 88" 3-ethylamino-pheno-black-blue black-blue li c> 9 !! 3-Octylamino-e-dark violet dark purple nole 9C 3-pyrrolidinophenol black-blue piperidinophenol dark blue dark blue 92 "3-dimethylamino-dark blue dark blue phenol 93 11 2-methyl-5-ethynyl gray blue-gray liaminophenol 94” 2-chloro-5-dimethyldark violet dark purple liaminophenol 1. ___ 58 432 22 fc .. ,, _____ ___, λ *

Development Coupling component Color obtained “« k- nent___ ki by air oxidation with 1 # 0 ^ ϊ ~ ta 95 2-dimethyl-3-hydroxyphenyl- · dark blue dark blue mino-4,5,6-Amine triaminopyrimide i in i "3-methylene cyano-dark purple dark purple amidophenol 97" 2-bromo-5 * -methyl- 'black-blue black-blue nicyanarindophenol:

98 "3-thioureidophenol brown-gray opaque violet 99" 4-methoxy-3-dimethane dark dark blue aminophenol β 2 -methyl-5-diethyl blue dark blue stylaminaminophenol 2-morpholino-4, md dimethylamine 6-Triaminophenol pyrimidine - * • 02 "3-hydroxyphenyl over-dark blue dark blue Amine ^ -O3" 3-octylamino-phenothet violet violet-blue noli 104 2-Piperyl, idin-imdimethylamino- dark blue dark blue 4,5 f 6-triamophenol nopyrimidine 105 "m-octylaminophenyl violet blue violet noli 106" 3-hydroxydiphenyl dark blue dark amine 107 2-methylamino-3-hydroxide if violet blue blue violet 5,6-Trinylamine aminopyrimidine 108 "3-Octylamino-deep purple deep purple phenol 109" m-dimethylamino-deep purple violet-blue phenol HO 2,4,5,6-tetra * 'md dimethylamino-dark purple dark purple aminopyrimiphenol dine 111 m-diethylamino dark purple dark purple phenol 112 "m-ethylaminophenoindigo blue indigo blue li X13" m-ethylpropyl-dark purple dark purple aminophenol XX4 "m-? 5-hydroxyethyl dark purple dark purple liaminophenol i_j-1-1-23 584 32

Pre * ___Development ....... ... Obtained color tone mark- Coupling component ----- [- ki atmospheric oxygen- with 1% H2C> 2 115 2,4,5,6-tet- m -piperidinophenol light violet-light-anion-aminopyrite braid mididine 116 "m-pyrrolidinophenol purple violet 117" 3-hydroxydiphenylindigonine-indigonsinylamine 118 2f4,5-triamino-naphthol reddish-brown - $ - hydroxy kea diethylaminopyrimidine 119 "2,4-diaminoanisole dark green dark green 120" resorcinol gray-reddish-gray manner 121 "resorcinol mono-brown gray-brown methyl ether 122" m-phenylenedi- olivine dark brown 124 "1,5-dihydroxy-brown gray-brown naphthalene 125 4,5-diamino-α-naphthol gray-bell-gray-yellow-2,6-bis-di-allyl methyl aminopyrimidine 126" 2/4-diaminoanisole olive-colored olive -i 127 "resorcinol brown- brownish red 128" resorcinol mono- light brown red isenkel methyl methyl larva 129 "m-phenylenediamine brown brown 130" m-aminophenol dark red-purple-brown kea 1 2 "1,5-dihydronaphthalate light brown light brown 2 line 24 584 32 ____

Pre- Development Obtained color tone_ sign- Switching component T! “F,„ J aeric acid: with 1% K 1 H 2 O 2 132 2,6-bis-di-α-naphthol olive gray-gray methylmethylamine lervo no-4-8-hydroxyethylamino -5-amino-pyrimidine 133 "resorcinol brown dark light gray 134" 2,4-diaminoanisole blue gray olive gray 135 "resorcinol monomer light brown brownish yellow ether 136" m-phenylenediamine yellowish brown light brown 137 "m-aminophenene -dihydroxy-olive-color-olive-brown naphthalene 139 2,4,6-Tris- [3- α-naphthol brown-red-hydroxyethyl ·· female amino-5-aminopyrimidine 140 "resorcinol gray-red 141" 2,4-diaminoanisole olive-colored olive brown 142 "resorcinol monomer light brown gray-yellow style ether 143" m-phenylenedi- brownish-yellow-green amine larva 144 "m-aminophenol dark red-brown-brown-brown not 145- 1/5-dihydroxy orange 146 2,6-bis-8-hyd-α-naphthol opaque red-brown-gray roxyethylamino-4-dimethylamino-5-aminopyrimidine 147 "resorcinol gray-red-brown-brown 148" 2,4-diaminoanisole opaque brown-gray female 1 2 "resorcinol monomer opaque reddish-brown 254 ether 2

Pre-Development The resulting hue is marked with a 1% H2 O2. "150 2,6-bis-β-hyd-m-phenylenediaramine red-brown-olive brown roxyethyl-amino-4-dimethylamino-5-aminopyrimidine 151" m-aminophenol gray-red-gray-brown ne n 152 "1, 5-Dihydroxy-gray-brown did not become naphthalene 153 2,6-Bis-β-hyd-α-naphthol red-brown-brown roxyethyl-amino-4-methylamino-5-aminopyrimidine 154 "resorcinol-brown red-brown kea 155 "2,4-diaminoanisole dark green olive brown 156" resorcinol monomer brown light brown style ether 157 "m-phenylenediamine yellow-brown dark green 158" m-aminophenol red-brown-yellow-brown-brown kea 1 "1,5-dihydroxy

To test the toxic and skin irritant properties of tetraaminopyrimidines, the experiments described below were performed. 2-Dimethylamino-4,5,6-triaminopyrrolidine sulfate was added as an experimental salt, which was added relative to p-phenylenediamine and p-toluenediamine sulfate. The following results were obtained.

1. Acute toxicity

General suitability experiments were performed on white CF / W 68 strain male mice. The average weight of the experimental animals was 22 g. Dosing of test substances was performed in increasing doses using a pharyngeal tube. The experiment included 10 mice at a time. The dose volume was constant at 0.2 cm 2/10 g live weight. After 8 days of observation, and by calculating the test results according to Litchfield - Wilcoxon (J. Iharm. Exptl., Ther., ^ 6 99-108 (1949)), the following LD, - ο value was obtained and: 2-dimethylamino-4,5,6 -triaminopyrimidine sulfate 555 mg / kg p-phenylenediamine 87 mg / kg p-toluenediamine sulfate. 110 mg / kg

Distilled water was used as a solvent.

2. Skin tolerance experiments in nude mice In groups of 5 animals per preparation, test substances were applied in 5% aqueous solutions once a day for 14 days with a small amount of back on the dirt. During treatment and at the end of the experiment, all animals were unresponsive.

3. Mucosal tolerance experiments in rabbit eyes These local tolerance experiments were performed by instilling small amounts of a 5? * Aqueous solution of the test substances into the conjunctiva of the eye of a group of Albino rabbits. Ocular mucosal reactions were evaluated at 2, 6, 24, and 48 hours according to Draize's scoring formula (Appraisal oi the safety of chemicals in foods, drugs and domestics. Ass. Of Food and Drug Officials of the UO, pp. 49-52 (1959 )). In this case, it was found that p-phenylenediamine leads to a slight reddening and irritation of the conjunctiva, which is no longer detectable 24 hours after instillation. Both other test substances did not cause reactions to this.

27 5 8432 li. Skin (tissue) tolerance tests in white mice with different concentrated intradermal single doses of test substances._ This Barail (j. Soc. Cosmet. CChemists 11, 2Ul (i960)) local tolerance test is based on low doses of test substance at increasing concentrations in white mice. . After 2 hours, the experimental animals are sacrificed, the treated skin areas are excised and dried. Skin lesions are graded according to a pie chart, taking into account bleeding and other lesions on the treated skin. Because a larger group of 10 mice was used per preparation and test concentration, even smaller differences in local tolerance can be observed with the previous test method. The test results are shown in Figure 1.

From the experimental results, it can be seen that 2-dimethylamino-1,5,6-triaminopyridine sulfate is the best of the tested developers in terms of general and local tolerance. In addition to these advantageous properties, the tetraaminopyriraidins used in the hair dyes according to the invention have the further advantage that color development can already be carried out with atmospheric oxygen and allows a wide range of color shades, which are characterized by good light, washing and abrasion resistance. easily removable.

Claims (3)

58432 28 Hair dye based on oxidative dyes, optionally also containing conventional developers and other dyes, characterized in that it contains tetraaminopyrimidines of the general formula R, ^ NN R1 \ N R2 ^ ^ \ where R 1 - R 9 denote hydrogen, an alkyl group having 1 to U carbon atoms, a group - (CH 2) - X in which n = 1 and X is a hydroxyl group, a halogen atom, a group -ΝΗΛ, 2 n 2 NHR 'and -NR'R "in which R' and R "may represent an alkyl group of 1 to k carbon atoms or together with a nitrogen atom a heterocyclic ring which may contain an additional nitrogen atom or an oxygen atom, an optionally substituted aryl group, an optionally substituted heterocyclic 5" or 6-membered ring having one or two nitrogen atoms, or nitrogen atom and oxygen atom and their inorganic or organic salts as developing agents and coupling agents. Hair dye according to Claim 1, characterized in that it contains tetraaminopyrimidines as developer and m-aminophenolenes of the general formula OH x ^ S1 "R 1 R 2 Y in which X and / or Y is hydrogen, a halogen atom, a hydroxyl group, an amino group, alkyl, alkoxy, alkylamino or dialkylamino group having 1 to U carbon atoms, R 1 is hydrogen, alkyl group having 1 to 10 carbon atoms, optionally substituted phenyl group, benzyl group, methylene cyanamide group, propionamido group, ureido group, thioureido group, oxalyl group having 1 carbon atom, a group (CH_) -Z, 2 n where n is a number 1-U and Z is a hydroxy group or a halogen atom, an amino group, NHR 'and NR'R ", wherein R' and R" denote an alkyl group in which is 1-U carbon atom 29 58432 m, in addition to which R 'and R "together with the nitrogen atom may form an optionally substituted heterocyclic 5- or 6-membered ring which may contain one additional nitrogen atom or oxygen atom, R 1 is the same as R 2, excluding hydrogen, and their inorganic or organic salts as coupling agents. Hair dye according to Claim 1 or 2, characterized in that it contains a total of 0.2 to 5% by weight of developer and coupling agent, preferably 1 to 3% by weight. 30 5 84 32